JPH11167204A - Photosensitive planographic printing plate and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive planographic printing plate which is good in plate wear, small dot reproducibility, the opening of the mesh of dots and dot gain when printing is executed under high-speed and severe conditions like those of rotary offset printing, is excellent in ball-point pen adaptability and obviates the erosion of the plate when printing is executed by using moistening water devoid of isopropyl alcohol. SOLUTION: An aluminum base is provided with undulations of 3 to 30 μm in the average wavelength of roughness or approximately spherical projections which are superposed with small pits having an average opening diameter of 0.2 to 3.0 μm in a congested form on large pits having an average opening diameter of 3 to 30 μm and has an average diameter of >=0.01 μm and below 1/2 the average opening diameter of the small pits within the small pits. This aluminum base is, thereupon, provided with a photosensitive layer contg. a o-naphthoquinone diazido sulfonic acid ester of an polycondensation resin of polyhydroxyphenol having a number average mol.wt. of 3.00×10<2> to 2.00×10<3> and a weight average mol.wt. of 5.00×10<2> to 4.00×10<3> and ketone or aldehyde and an alkali-soluble resin, by which this printing plate is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a photosensitive lithographic printing plate and a method for producing the same.

[0002]

2. Description of the Related Art In recent years, the printing speed of a printing machine has been increased in order to improve the productivity of printed matter. Such a phenomenon is particularly remarkable in the field of offset rotary printing. Since such high-speed printing is severe as a printing condition,
The endurance of printed sheets is reduced, image lines on printed matter, particularly, the attachment of halftone dots (that is, the reproducibility of small dots) is deteriorated, or the halftone dots are partially crushed (that is, the halftone dots are not open). Bad) or the dot gain further deteriorates.

[0003] In an offset printing press, printing is performed by utilizing the property that oil-based ink and water repel each other. The offset printing machine is provided with a dampening part on the plate, and gives water called dampening water from the dampening part to the plate,
Water is attached to the hydrophilic non-image area so that the oil-based ink does not stick to the lipophilic image area. The water also plays a role in moistening the plate to prevent contamination by ink, and maintaining a constant plate surface temperature.

[0004] The dampening solution usually lowers the surface tension of the water,
Isopropyl alcohol (hereinafter referred to as "IPA") is added to make the plate easily wettable. However, in recent years, it has been desired to reduce or eliminate environmental pollutants such as isopropyl alcohol from the viewpoint of environmental protection, and IPA-free dampening water is being generally used. When printing is performed using such an IPA-free dampening solution and the printing press is temporarily stopped during a lunch break or the like, since the dampening solution is left attached to the plate, the photosensitive layer, which is the image portion of the plate, cannot be used. There is a problem that an image is not formed on a printed matter when printing is resumed due to erosion.

On the other hand, in the process of exposing a photosensitive lithographic printing plate to an image, when performing so-called multi-sided printing in which a plurality of original films are printed one after another at different positions, the position of the original is exposed to align the original films. Although sometimes marked on the layer, an oil-based ballpoint pen is commonly used as a writing instrument for this mark. If the marked part is a non-image part, if developed as it is, the photosensitive layer in the non-image part is dissolved and removed, the mark with an oil-based ballpoint pen remains on the grain, ink adheres during printing, and the mark mark is reproduced on the printed matter Failure (suitability for ballpoint pen). Therefore, there is a demand for a photosensitive lithographic printing plate which does not cause such a problem, that is, has excellent suitability for a ball-point pen.

As a result of various studies in view of the above problems, the inventors have found that the above-mentioned objects can be achieved by the inventions of claims 1 to 14 described later, and have completed the present invention. Things.

[0007]

SUMMARY OF THE INVENTION A first object of the present invention is to provide a photosensitive lithographic printing plate having good printing durability when printing under high-speed and severe printing conditions such as offset rotary printing. That is.

A second object of the present invention is to provide a photosensitive lithographic printing plate having good small dot reproducibility when printing under high-speed and severe printing conditions such as offset rotary printing.

[0009] A third object of the present invention is to provide a photosensitive lithographic printing plate having excellent suitability for a ball-point pen.

[0010] A fourth object of the present invention is to provide a photosensitive lithographic printing plate which will not be attacked by printing using a fountain solution containing no isopropyl alcohol.

A fifth object of the present invention is to provide a photosensitive lithographic printing plate having good halftone dots when printed under high-speed and severe printing conditions such as offset rotary printing. .

A sixth object of the present invention is to provide a photosensitive lithographic printing plate having a good dot gain when printing under severe printing conditions at high speed such as offset rotary printing.

[0013]

The above object is achieved by the following (1) to (4).
This is achieved by any one of (14).

(1) Small pits having an average opening diameter of 0.2 to 3.0 μm are densely superimposed on large pits having an average roughness of 3 to 30 μm or a large pit having an average opening diameter of 3 to 30 μm. The number average molecular weight is 3.0 on an aluminum support having a substantially spherical projection having an average diameter of 0.01 μm or more and 1/2 or less of the average opening diameter of the small pit inside the small pit.
0 × 10 ^{2 to} 2.00 × 10 ³ , weight average molecular weight of 5.0
A layer of a photosensitive composition containing o-naphthoquinonediazidosulfonic acid ester of polycondensation resin of 0 × 10 ^{2 to} 4.00 × 10 ³ with polyhydroxyphenol and ketone or aldehyde, and an alkali-soluble resin; A photosensitive lithographic printing plate characterized by the following.

(2) Small pits having an average opening diameter of 0.2 to 3.0 μm are densely superimposed on large pits having an average roughness of 3 to 30 μm or a large pit having an average opening diameter of 3 to 30 μm. A structural unit represented by the following general formula (1) is formed on an aluminum support having a substantially spherical protrusion having an average diameter of 0.01 μm or more and 1/2 or less of the average opening diameter of the small pit inside the small pit. A polymer compound having in the structure;
A photosensitive lithographic printing plate comprising a layer of a photosensitive composition containing an o-quinonediazide compound.

[0016]

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(Wherein R ₁ and R ₂ are a hydrogen atom, an alkyl group or a carboxyl group, R ₃ is a hydrogen atom, a halogen atom or an alkyl group, R ₄ is a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group, A Represents a divalent organic group linking a nitrogen atom and an aromatic ring carbon atom, m represents 0 or 1, and B represents a phenylene group which may have a substituent or a naphthylene group which may have a substituent. (3) Undulation with an average roughness of 3 to 30 μm or large pits with an average opening diameter of 3 to 30 μm having an average opening diameter of 0.3 to 30 μm.
Small pits of 2 to 3.0 μm are densely superimposed, 0.01 μm or more inside the small pits, and 1 / of the average small pit opening diameter.
A resin obtained by copolycondensation of phenol and m-, p-mixed cresol and aldehyde on an aluminum support having a substantially spherical projection having an average diameter of 2 or less,
A resin having a molar ratio of the phenol to the m-, p-mixed cresol of 1: 9 to 9: 1 and a layer of a photosensitive composition containing an o-quinonediazide compound are provided. Photosensitive lithographic printing plate.

(4) Small pits having an average opening diameter of 0.2 to 3.0 μm are densely superimposed on large pits having an average roughness of 3 to 30 μm or undulations or an average opening diameter of 3 to 30 μm. An o-quinonediazide compound represented by the following general formula (2) is formed on an aluminum support having a substantially spherical projection having an average diameter of 0.01 μm or more and 1/2 or less of the average opening diameter of small pits inside the small pits. A photosensitive composition comprising a layer of a photosensitive composition containing an s-triazine compound, a colorant that changes color tone by interaction with a photolysis product of the s-triazine compound, and an alkali-soluble resin. Print version.

[0019]

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(Wherein, R ₁ and R ₂ each represent an alkyl group, a substituted alkyl group, an alkoxy group, a substituted alkoxy group or a hydrogen atom. R ₃ and R ₄ each represent 1 carbon atom.
Represents a haloalkyl group or haloalkenyl group having from 3 to 3; (5) The average opening diameter of a large pit having an undulation or an average opening diameter of 3 to 30 μm is 3 to 30 μm.
Small pits of 2 to 3.0 μm are densely superimposed, 0.01 μm or more inside the small pits, and 1 / of the average small pit opening diameter.
A compound having at least one ethylenically unsaturated double bond capable of addition polymerization, a compound having an aromatic hydroxyl group in a side chain, and / or a compound having at least one ethylenically unsaturated double bond capable of addition polymerization on an aluminum support having substantially spherical projections having an average diameter of 2 or less. Or a layer of a photosensitive composition containing an acidic vinyl copolymer soluble or swellable in alkaline water, a photopolymerization initiator, and a diazo resin, containing a compound having an aliphatic hydroxyl group in a side chain as a constituent unit in the molecule. A photosensitive lithographic printing plate characterized by comprising:

(6) Small pits having an average opening diameter of 0.2 to 3.0 μm are densely superimposed on large pits having an average roughness of 3 to 30 μm or undulations or an average opening diameter of 3 to 30 μm. An acid generator, an acid-decomposable compound, and an infrared absorber are contained on an aluminum support having roughly spherical projections having an average diameter of 0.01 μm or more and 1/2 or less of the average opening diameter of the small pits inside the small pits. A photosensitive lithographic printing plate provided with a layer of a photosensitive composition.

(7) Small pits having an average opening diameter of 0.2 to 3.0 μm are densely superimposed on large pits having an average roughness of 3 to 30 μm or undulations having an average opening diameter of 3 to 30 μm, An acid generator, a compound insolubilized by an acid, and an infrared absorber on an aluminum support having a substantially spherical projection having an average diameter of 0.01 μm or more and 1/2 or less of the average opening diameter of the small pit inside the small pit A photosensitive lithographic printing plate provided with a layer of a photosensitive composition containing:

(8) The average opening diameter of the small pits is 0.2 to
Any of (1) to (7) above, wherein the average diameter of the roughly spherical projections inside the small pit is not less than 0.01 μm and not more than １ ／ of the average small pit opening diameter. 1
A photosensitive lithographic printing plate according to the item.

(9) The photosensitive lithographic printing plate as described in (8) above, wherein the ratio of the pit depth to the small pit opening diameter is 0.2 or less.

(10) The photosensitive lithographic printing as described in any one of (1) to (9) above, wherein a space between the substantially spherical projections inside the small pits is formed as a smooth surface. Edition.

(11) The surface of the aluminum plate is mechanically roughened or degreased and then electrolytically roughened, subjected to a surface dissolving treatment with an alkali, neutralized with an acid, and electrolytically roughened in an acidic electrolytic solution.
Further, after performing a surface dissolution treatment with an alkali, neutralizing with an acid, and performing an anodization treatment, a metal oxide coating obtained by hydrolyzing and polycondensing an organic metal compound or an inorganic metal compound on the anodized film. Layer, and the above (1) to
(7) A method for producing a photosensitive lithographic printing plate, comprising providing the layer of the photosensitive composition according to any one of the above (7).

(12) The method for producing a photosensitive lithographic printing plate as described in (11) above, wherein the electrolyte mainly comprises hydrochloric acid and / or acetic acid.

(13) The surface of the aluminum plate is subjected to dissolution treatment with an alkali, neutralized with an acid, electrolytically roughened in an acidic electrolyte mainly composed of hydrochloric acid and / or acetic acid, and the surface is further dissolved with an alkali. After neutralizing with an acid and performing anodizing treatment, a metal oxide coating layer obtained by hydrolyzing and polycondensing an organometallic compound or an inorganic metal compound is provided on the anodized film, and the above-mentioned ( A method for producing a photosensitive lithographic printing plate, comprising providing a layer of the photosensitive composition according to any one of (1) to (7).

(14) Electrolytic treatment is performed so that a part where the electrolytic treatment progresses rapidly and a part where the electrolytic treatment progresses slowly or stops are alternately present a plurality of times in all the steps of electrolytic surface roughening; (13) The method for producing a photosensitive lithographic printing plate as described in (13) above, wherein the amount of electricity of the electrolytic treatment in one part of the step where the electrolytic treatment progresses rapidly is 100 C / dm ² or less on average.

Hereinafter, the present invention will be described in detail.

An o-naphthoquinonediazidosulfonic acid ester compound of the polycondensation resin having the specific number average molecular weight and weight average molecular weight of polyhydroxyphenol and ketone or aldehyde contained in the photosensitive composition of the present invention according to claim 1. Is a compound as shown below.

As the polyhydroxyphenol which is a monomer of the backbone polymer, catechol, (methyl) resorcin, hydroquinone, pyrogallol, phloroglucin and the like are preferably used. Further, more preferred is pyrogallol. As the ketone or aldehyde, acetone, formaldehyde, acetaldehyde, benzaldehyde, crotonaldehyde and the like are preferably used, and acetone is more preferable.

As a method for synthesizing a polycondensation resin of polyhydroxyphenol and ketone or aldehyde, a generally known method is applied, and polyhydroxyphenol is dissolved in ketone or aldehydes or, if necessary, an appropriate solvent. Polycondensation is performed under a suitable acid such as hydrochloric acid, phosphorus oxychloride, oxalic acid, etc. to obtain a polymer. As a polycondensation condition, a synthesis method in which a polycondensation reaction is carried out at a high temperature from the initial stage of polymerization is preferably used, as compared with a known method. For example, as a catalyst, hydrochloric acid, sulfuric acid, oxalic acid, an acid such as phosphorus oxychloride is dropped into a mixture of polyhydroxyphenol and a ketone or an aldehyde compound, a solvent used as needed, for example, dioxane, methanol, ethanol, and aqueous tetrahydrofuran. At the same time, a formulation brought to a steady state of reflux is preferably used. The molecular weight of the polyhydroxy polymer compound obtained by these methods is 3.00 × 10 ^{2 as the} number average molecular weight Mn (polystyrene standard) determined by the GPC method.
2.00 × 10 ³ , 5.00 × 10 ³ in weight average molecular weight Mw
10 ^{2 to} 4.00 × 10 ³ are used, and more preferably M
n is 4.00 × 10 ^{2 to} 1.50 × 10 ³ , and Mw is 7.0
0 × 10 ^{2 to} 3.00 × 10 ³ , more preferably Mn is 5.
00 × 10 ^{2 to} 1.10 × 10 ³ , Mw is 8.00 × 10
^{2 to} 2.00 × 10 ³ .

When Mn is larger than 2.00 × 10 ³ and M
When using o-naphthoquinonediazidesulfonic acid ester of a polyhydroxyphenol polymer having w larger than 4.00 × 10 ³ , Mn is smaller than 3.00 × 10 ² and Mn is smaller than 5.00 × 10 ^2. Even when o-naphthoquinonediazidosulfonic acid ester of polyhydroxyphenol polymer is used, satisfactory printing durability cannot be obtained when printing is performed at high speed and under severe printing conditions such as offset rotary printing.

Preferred examples of the polyhydroxyphenol polymer which can obtain a satisfactory printing durability when printing under high-speed and severe printing conditions such as offset rotary printing are:
Resorcin benzaldehyde resin, methylresorcin benzaldehyde, pyrogallol / acetone resin having the above molecular weight range, and more preferably pyrogallol / acetone resin. The o-naphthoquinonediazidosulfonic acid ester of these polyhydroxyphenol polymers can be easily obtained by the following synthesis method.

A polymer of polyhydroxyphenol is dissolved in an appropriate solvent, for example, dioxane, and o-naphthoquinonediazidosulfonic acid chloride is added thereto. Is done.

The condensation rate of o-naphthoquinonediazide sulfonic acid chloride with respect to OH groups of this esterified product is preferably 20 to 80% (% based on one OH group), more preferably 25 to 70%, and further preferably 30 to 70%. 60
%.

Although the molecular weight of the esterified product slightly varies depending on the condensation rate of OH groups, it is generally 20%.
For the esterified product from mol% to 70 mol%, Mn
Is 5.00 × 10 ^{2 to} 2.60 × 10 ³ and Mw is 7.00.
It is preferably from × 10 ^{2 to} 4.80 × 10 ³ , and more preferably Mn is 6.00 × 10 ^{2 to} 2.40 × 10 ³ and Mw is 9.
It is from 00 × 10 ^{2 to} 4.00 × 10 ³ . More preferably, Mn is 7.00 × 10 ^{2 to} 2.10 × 10 ³ and Mw is 1.
It is from 00 × 10 ^{3 to} 3.60 × 10 ³ . The content of the esterified compound in the photosensitive layer varies depending on the kind thereof, but is generally preferably 5 to 40% by weight, more preferably 10 to 30% by weight.

As the alkali-soluble resin used in the first aspect of the invention, any of the following alkali-water-soluble resins can be used, but a novolak resin is preferable.

Resins soluble in alkaline water are used as binders, and specifically, phenol formaldehyde resins, o-, m- and p-cresol formaldehyde resins, and m- / p-mixed cresol formaldehyde resins , Phenol / cresol (o-, m-, p
-, M- / p- and o- / m-). Novolak resins such as mixed formaldehyde resins, phenol-modified xylene resins, polyhydroxystyrene, polyhalogenated hydroxystyrene, JP-A-51-34771
Acrylic resins containing a phenolic hydroxyl group described in No. 1 are exemplified.

As other suitable alkali-soluble resins, the following monomers are used as constituent units, and the molecular weight is 10,000 to
200,000 copolymers can be mentioned.

(1) Acrylamides, methacrylamides, acrylates, methacrylates, hydroxystyrenes having an aromatic hydroxyl group;
(4-hydroxyphenyl) acrylamide, N- (4
-Hydroxyphenyl) methacrylamide, o-, m-
Or p-hydroxystyrene, o-, m- or p-hydroxyphenyl acrylate or methacrylate; (2) acrylates and methacrylates having an aliphatic hydroxyl group; 2-hydroxyethyl acrylate or methacrylate; (3) acryl Unsaturated carboxylic acids such as acid, methacrylic acid, maleic anhydride, and methaconic acid (4) Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, cyclohexyl acrylate, acrylic acid Octyl, phenyl acrylate, benzyl acrylate, 2-chloroethyl acrylate, 4-acrylic acid
(Substituted) acrylates such as hydroxybutyl, glycidyl acrylate, N-dimethylaminoethyl acrylate, etc. (5) Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate (Substituted) methacrylates such as octyl methacrylate, phenyl methacrylate, benzyl methacrylate, 2-chloroethyl methacrylate, 4-hydroxybutyl methacrylate, glycidyl methacrylate, N-dimethylaminoethyl methacrylate, (6) acrylamide, Methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N-ethylacrylamide, N-ethylmethacrylamide, N-hexyl Acrylamide, N- hexyl methacrylamide, N- cyclohexyl acrylamide,
N-cyclohexylmethacrylamide, N-hydroxyethylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-phenylmethacrylamide, N-benzylacrylamide, N-benzylmethacrylamide, N-nitrophenylacrylamide, N-nitrophenyl Methacrylamide, N-ethyl-N-phenylacrylamide, N-ethyl-N-
Acrylamide or methacrylamide such as phenyl methacrylamide; (7) vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, and phenyl vinyl ether; (8) vinyl acetate, vinyl chloroacetate; Vinyl esters such as vinyl butyrate and vinyl benzoate (9) Styrenes such as styrene, methyl styrene and chloromethyl styrene (10) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone and phenyl vinyl ketone ( 11) Olefins such as ethylene, propylene, isobutylene, butadiene, isoprene, etc. (12) N-vinylpyrrolidone, N-vinyl Rubazole, 4-vinylpyridine, acrylonitrile, methacrylonitrile, etc. (13) N- (o-aminosulfonylphenyl) acrylamide, N- (m-aminosulfonylphenyl) acrylamide, N- (p-aminosulfonylphenyl) acrylamide, N Acrylamides such as-[1- (3-aminosulfonyl) naphthyl] acrylamide, N- (2-aminosulfonylethyl) acrylamide;
(O-aminosulfonylphenyl) methacrylamide,
N- (m-aminosulfonylphenyl) methacrylamide, N- (p-aminosulfonylphenyl) methacrylamide, N- [1- (3-aminosulfonyl) naphthyl] methacrylamide, N- (2-aminosulfonylethyl) methacryl Methacrylamides such as amides; o-
Unsaturated sulfonamides such as acrylates such as aminosulfonylphenyl acrylate, m-aminosulfonylphenyl acrylate, p-aminosulfonylphenyl acrylate and 1- (3-aminosulfonylphenylnaphthyl) acrylate; o-aminosulfonylphenyl methacrylate And unsaturated sulphonamides such as methacrylic acid esters such as m-aminosulfonylphenyl methacrylate, p-aminosulfonylphenyl methacrylate, 1- (3-aminosulfonylphenylnaphthyl) methacrylate.

Further, a copolymer obtained by copolymerizing the above-mentioned monomer and modified with glycidyl acrylate, glycidyl methacrylate or the like is also included.

These copolymers preferably contain the unsaturated carboxylic acids listed in (3), and the copolymer preferably has an acid value of 0 to 10 meq / g, more preferably 0.2 to 10 meq / g.
It is 5.0 meq / g. The preferred molecular weight of these copolymers is 10,000 to 100,000. If necessary, a polyvinyl butyral resin, a polyurethane resin, a polyamide resin, or an epoxy resin may be added to these copolymers.

The alkali-soluble resin is 80% of the photosensitive composition.
It is used at less than% by weight.

The polymer compound having the structural unit represented by the general formula (1) in the molecular structure of the invention according to claim 2 (hereinafter referred to as “polymer compound A”) is non-photosensitive and has a molecular structure Characterized by having a structural unit represented by the general formula (1), and a homopolymer type having a repeating structure of only the structural unit, or an unsaturated double bond of the structural unit and another vinyl monomer. Is a copolymer type structure having a repeating structure obtained by combining at least one structural unit represented by a structure obtained by cleaving. Examples of the structural unit used in combination with the structural unit represented by the general formula in the polymer compound of the present invention having a copolymer type structure include, for example, ethylene, propylene, isobutylene, butadiene, and ethylenically unsaturated olefins such as isoprene. For example, styrenes such as styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene and the like, for example, acrylic acids such as acrylic acid and methacrylic acid, for example, butanols such as itaconic acid, maleic acid and maleic anhydride. Saturated aliphatic dicarboxylic acids, for example, methyl acrylate,
Ethyl acrylate, n-butyl acrylate, isobutyl acrylate, dodecyl acrylate, acrylic acid-2-
Chloroethyl, phenyl acrylate, α-methyl methyl acrylate, methyl methacrylate, ethyl methacrylate, esters of α-methylene aliphatic monocarboxylic acids such as ethyl ethacrylate, for example, acrylonitrile, nitriles such as methacrylonitrile, for example , Amides such as acrylamide, for example, acrylanilide, p-
Anilides such as chloroacrylanilide, m-nitroacrylanilide and m-methoxyacrylanilide; for example, vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate and vinyl acetate; for example, methyl vinyl ether, ethyl vinyl ether and isobutyl Vinyl ethers, vinyl ethers such as β-chloroethyl vinyl ether, vinyl chloride, vinylidene chloride, vinylidene cyanide, for example, 1-methyl-1-
Methoxyethylene, 1,1-dimethoxyethylene, 1,
Ethylene derivatives such as 2-dimethoxyethylene, 1,1-dimethoxycarbonylethylene, 1-methyl-1-nitroethylene, for example, N-vinylpyrrole, N-vinylcarbazole, N-vinylindole, N-vinylpyrrolidene, There are N-vinyl monomers such as N-vinylpyrrolidone. These monomers are present in the polymer compound in a structure in which the unsaturated double bond is cleaved.

Among the above-mentioned monomers, esters and nitriles of aliphatic monocarboxylic acids exhibit excellent performance for the purpose of the present invention and are preferred.

These monomers may be bonded to the molecular structure of the polymer compound A in either a block or random state.

In the structural unit of the polymer compound A represented by the general formula (1), B represents a phenylene group which may have a substituent or a naphthylene group which may have a substituent.
Since the characteristics of the photosensitive composition of the present invention are hardly greatly affected by the type of the substituent, any group can be used as the substituent. Representative substituents include, for example, alkyl groups, alkoxy groups, halogen atoms, acyl groups, hydroxyl groups, carboxyl groups, sulfonic groups, cyano groups, nitro groups, and the like. Next, typical specific examples of the polymer compound of claim 2 will be described. In the following exemplified compounds, Mn represents an average molecular weight, and k, l, m and n represent mol% of each structural unit.

Next, typical specific examples of the polymer compound A will be described. In the following exemplified compounds, Mn represents an average molecular weight, and k, l, m and n represent mol% of each structural unit.

[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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The polymer compound A is synthesized as follows. That is, α · β-unsaturated acid chlorides or α · β
A first having unsaturated acid anhydrides and a phenolic hydroxyl group;
After reacting a secondary or secondary amine with a basic catalyst, if necessary, to synthesize a monomer having a structure corresponding to the structural unit represented by the above general formula, The polymer compound of the present invention can be obtained by homopolymerizing according to the method or copolymerizing the monomer with at least one of other vinyl monomers. On this occasion,
The molecular weight and the molar ratio of each structural unit can be obtained as arbitrary values over a wide range by variously changing the charged molar ratio of each monomer and polymerization conditions, but the object of the present invention, such as offset rotary printing, can be obtained. In order to effectively provide good small dot reproducibility when printing under severe printing conditions at high speed, the molecular weight should be about 5,000 to 100,000, and the molar content of the structural unit represented by the above general formula should be at least 1
It is desirably 0 mol%.

In the invention according to claim 2, o-quinonediazide compound represented by o-quinonediazide compound contained in the photosensitive composition
-Naphthoquinonediazide compounds. Examples of the o-naphthoquinonediazide compound include JP-B-43-284.
An ester of 1,2-diazonaphthoquinonesulfonic acid and a pyrogallol-acetone resin described in No. 03 is preferred. U.S. Pat. Nos. 3,046,120 and 3,18
No. 8,210, 1,2-diazonaphthoquinone-5
Esters of sulfonic acid and phenol / formaldehyde resin, JP-A-2-96163, JP-A-2-96165
Esters of 1,2-diazonaphthoquinone-1-sulfonic acid with phenol / formaldehyde resin described in JP-A-47-5303 and JP-A-2-96671.
No. 13854, No. 48-63802, No. 48-63
Nos. 803, 48-96575, 49-38001
No., JP-B-37-18015, 41-11222
Nos. 45-9610 and 49-17481, U.S. Pat. Nos. 2,797,213 and 3,453,400.
Nos. 3,544,323 and 3,573,917
Nos. 3,674,495 and 3,785,825
No., British Patent Nos. 1,227,602 and 1,251,
No. 345, No. 1, 267, 005, No. 1, 329, 8
Nos. 88 and 1,330,932, German Patent No. 85
No. 4,890, etc. are also preferably used.

Although the o-quinonediazide compound alone forms the photosensitive layer, it is preferable to use a resin which is soluble in alkaline water as a binder. As the resin, an alkali-soluble resin contained in the photosensitive composition according to the first aspect of the present invention can be used.

The co-condensate of phenol and m-, p-mixed cresol with aldehyde used in the invention according to claim 3 is obtained by polycondensing a mixture of phenol and m-, p-mixed cresol with aldehyde. be able to. The mixing ratio of phenol and m-, p-mixed cresol is preferably in the range of 1: 9 to 9: 1 in molar ratio. 1: 9
Satisfactory ballpoint pen suitability cannot be obtained even if the phenol ratio is lower or the phenol ratio is higher than 9: 1.

The aldehyde to be polycondensed with phenol and m-, p-mixed cresol includes aliphatic and aromatic aldehydes such as formaldehyde, acetaldehyde, acrolein, and furfural. The molecular weight of the co-condensate is preferably from 700 to 6000 in terms of weight average molecular weight. The content of the resin of the present invention obtained by copolycondensing phenol and m-, p-mixed cresol with aldehyde is preferably 40 to 80% by weight based on the total solid content in the photosensitive composition.

As the o-quinonediazide compound used in the third aspect of the invention, the o-quinonediazide compound of the second aspect can be used.

As the o-quinonediazide compound used in the invention according to claim 4, the o-quinonediazide compound according to the invention according to claim 2 can be used.

The s-triazine compound used in the invention according to claim 4 is a 2,4-triazine compound represented by the general formula (2).
Bis (haloalkyl or haloalkenyl) -6-substituted styryl-s-triazine compounds. The haloalkyl group or haloalkenyl group of the s-triazine is substituted with one or more halogen atoms. These s
-Triazine can be synthesized by a known method. For example, it is obtained by a condensation reaction of 2,4-bis (haloalkyl or haloalkenyl) -6-methyl-s-triazine and the corresponding aromatic aldehyde according to the method described in JP-A-48-36281. Can be Suitable aldehydes include p-methoxybenzaldehyde,
p-ethoxybenzaldehyde, p-propoxybenzaldehyde, p-butoxybenzaldehyde, p-pentyloxybenzaldehyde, p-methylbenzaldehyde, p-ethylbenzaldehyde, p-propylbenzaldehyde, p-butylbenzaldehyde, p-pentylbenzaldehyde, o-methoxybenzaldehyde , O-ethoxybenzaldehyde, o-propoxybenzaldehyde, o-butoxybenzaldehyde, o-
Pentyloxybenzaldehyde, o-methylbenzaldehyde, o-ethylbenzaldehyde, o-propylbenzaldehyde, o-butylbenzaldehyde, o-
Pentylbenzaldehyde, o, p-dimethoxybenzaldehyde, o, p-diethoxybenzaldehyde,
o, p-dipropoxybenzaldehyde, o, p-dibutoxybenzaldehyde, o, p-dipentyloxybenzaldehyde, o, p-dimethylbenzaldehyde,
o, p-Diethylbenzaldehyde, o, p-dipropylbenzaldehyde, o, p-dibutylbenzaldehyde, o, p-dipentylbenzaldehyde and the like.

When R ₁ and R ₂ represent an alkyl group or an alkoxy group, it preferably has 1 to 4 carbon atoms. Even when the carbon chain of the alkyl group or the alkoxy group is linear, It may have a chain. Further, as the halogen atom contained in R ₃ and R ₄ , a chlorine atom or a bromine atom is generally suitable, and more preferably, R ₃ and R ₄ each represent a trihaloalkyl group or a trihaloalkenyl group. More preferably, R ₃ and R ₄ each represent a trichloromethyl group.

Of these, 2,4-bis (trichloromethyl) -6- (p-alkoxystyryl) -s-triazine and 2,4-bis (trichloromethyl) -6- (p-alkyl Styryl) -s-triazine, 2,4-bis (trichloromethyl) -6- (o, p
-Dialkylstyryl) -s-triazine and 2,4-
Bis (trichloromethyl) -6- (o, p-dialkoxystyryl) -s-triazine. Specific examples of the s-triazine compound represented by the general formula (II) are shown below, but the s-triazine compound used in the present invention is not limited to these specific examples. Unless otherwise described in the following examples, R ₁ and R ₂ each represent a hydrogen atom, and R ₃ and R ₄ each represent a trichloromethyl group.

(2-1) R ₁ : methoxy group (2-2) R ₁ : ethoxy group (2-3) R ₁ : propoxy group (2-4) R ₁ : butoxy group (2-5) R ₂ : Methoxy group (2-6) R ₂ : ethoxy group (2-7) R ₂ : propoxy group (2-8) R ₂ : butoxy group (2-9) R ₁ and R ₂ : methoxy group (2-10) R ₁ and R ₂ : ethoxy group (2-11) R ₁ and R ₂ : propoxy group (2-12) R ₁ and R ₂ : butoxy group (2-13) R ₁ : methyl group (2-14) R _1: ethyl (2-15) R _1: propyl (2-16) R _1: butyl group (2-17) R _2: methyl (2-18) R _2: ethyl (2-19) R ₂ : propyl group (2-20) R ₂ : butyl group (2-21) R ₁ and R ₂ : methyl group (2-22) R ₁ and R ₂ : d Cyl group (2-23) R ₁ and R ₂ : propyl group (2-24) R ₁ and R ₂ : butyl group The addition amount of these halomethyl s-triazine compounds is
In general, 0.05 to the total solid content of the photosensitive composition.
10 to 10% by weight is suitable, preferably 0.1 to 5%.
% By weight.

In the invention according to claim 4, as the colorant which changes its color tone by interacting with the photolysis product of the s-triazine compound represented by the general formula (2), a color-forming dye and a color fading or discoloration And two types. As the dye which fades or discolors, for example, various dyes such as diphenylmethane dye, triphenylmethane dye, thiazine dye, oxazine, xanthene, anthraquinone, iminonaphthoquinone, azomethine and the like are effectively used.

Examples of the coloring dye include, for example, arylamines. Arylamines suitable for this purpose include simple arylamines such as primary and secondary aromatic amines, as well as so-called leuco dyes.

In the invention according to claim 4, the alkali-soluble resin represented as the alkali-soluble resin includes the alkali-soluble resin in the invention according to claim 1 described above.
An alkali-soluble resin used for a positive photosensitive layer containing a quinonediazide compound as a photosensitive component can be used.

[0070] In the invention according to claims 1 to 4, the layer of the photosensitive composition may further comprise US Pat. No. 4,123,279.
As described in the above item, the combined use of a condensate of phenol having an alkyl group having 3 to 8 carbon atoms as a substituent, such as t-butylphenol formaldehyde resin and octylphenol formaldehyde resin, with formaldehyde improves the oil sensitivity of the image. This is preferred. Also, in the photosensitive composition, to enhance the sensitivity cyclic acid anhydrides,
It is preferable to add phenols and organic acids.

As the cyclic anhydride, US Pat.
Phthalic anhydride described in Patent 5,128, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3,6-oxy - [delta ⁴ - tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, maleic acid anhydride, chlorosulfonic maleic anhydride, α-phenyl maleic anhydride, succinic anhydride, pyromellitic anhydride and the like can be used.

Phenols include bisphenol A, p-nitrophenol, p-ethoxyphenol,
2,4,4'-trihydroxybenzophenone, 2,
3,4-trihydroxybenzophenone, 4-hydroxybenzophenone, 4,4 ', 4 "-trihydroxy-
Triphenylmethane, 4,4 ', 3 ", 4"-tetrahydroxy-3,5,3',5'-tetramethyltriphenylmethane and the like.

As the organic acids, JP-A-60-8894
2, sulfonic acids, sulfinic acids, alkyl sulfates, phosphonic acids described in JP-A-2-96755 and the like;
Phosphoric acid esters and carboxylic acids and the like, specifically, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, p-toluenesulfinic acid, ethyl sulfate, phenylphosphonic acid, phenylphosphinic acid, phenyl phosphate, phenyl phosphate, diphenyl phosphate, Benzoic acid, isophthalic acid, adipic acid, p-toluic acid, 3,4-dimethoxybenzoic acid,
Phthalic acid, terephthalic acid, 1,4-cyclohexene-
Examples thereof include 2,2-dicarboxylic acid, erucic acid, lauric acid, n-undecanoic acid, and ascorbic acid.

The proportion of these cyclic acid anhydrides, phenols and organic acids in the photosensitive composition is 0.05 to 15%.
% By weight, preferably 0.1 to 5% by weight.

Further, in order to increase the processing stability (development latitude) in the photosensitive composition regardless of the development conditions,
Nonionic surfactants described in JP-A-62-251740, JP-A-59-121044, JP-A-4-131
An amphoteric surfactant described in No. 49 can be added. Specific examples of the nonionic surfactant include sorbitan tristearate, sorbitan monopalmitate, sorbitan triolate, stearic acid monoglyceride,
Examples thereof include polyoxyethylene sorbitan monooleate and polyoxyethylene nonylphenyl ether. Specific examples of the amphoteric surfactant include alkyl di (aminoethyl) glycine, alkyl polyaminoethyl glycine hydrochloride, 2-alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine and N-tetradecyl-N, N- Betaine type (for example, Daiichi Kogyo Co., Ltd.)
Manufactured by Amogen K), alkyl imidazoline (manufactured by Sanyo Chemical Co., Ltd .: Levon 15) and the like. The ratio of these surfactants in the photosensitive composition is 0.05 to 15%.
% By weight, and more preferably 0.1 to 5% by weight.

Further, a printing-out agent for obtaining a visible image immediately after exposure, and a dye or pigment as an image coloring agent can be added to the photosensitive composition. As a baking agent,
Combinations of compounds that release acid upon exposure (photoacid releasing agents) and organic dyes capable of forming salts, specifically, o-type compounds described in JP-A-50-36209 and JP-A-53-8128.
Combinations of naphthoquinonediazide-4-sulfonic acid halogenides with salt-forming organic dyes and JP-A-53-362
No. 23, No. 54-74728, No. 60-3626,
The combinations of the trihalomethyl compounds and the salt-forming organic dyes described in JP-A-61-143748, JP-A-61-151644, and JP-A-63-58440 can be mentioned as representatives. Trihalomethyl compounds include oxazole-based compounds and triazine-based compounds, both of which are excellent in stability over time and give clear print-out images.

As the colorant for the image, other dyes can be used in addition to the above-mentioned salt-forming organic dyes. Suitable dyes, including salt-forming organic dyes, include oil-soluble dyes and basic dyes. Specifically, Oil Yellow # 101, Oil Yellow # 103, Oil Pink # 312, Oil Green BG, Oil Blue BOS,
Oil Blue # 603, Oil Black BY, Oil Black BS, Oil Black T-505 (all manufactured by Orient Chemical Co., Ltd.), Victoria Pure Blue, Crystal Violet (CI42555), Methyl Violet (CI42535), Ethyl Violet, Rhodamine B (CI45170B), malachite green (CI42000), methylene blue (CI5201)
5) and the like. Also, JP-A-62-293
The dye described in No. 247 is particularly preferred.

The photosensitive composition dissolves each of the above components,
For example, it is dissolved and dispersed in a solvent as described in JP-A-62-251739 at a solid content of 2 to 50% by weight,
It is coated on a support at a weight of 0.3 to 4.0 g / m ² after drying and dried. In the photosensitive composition, a surfactant for improving the coating surface quality, for example, JP-A-62-17
No. 0950 can be added. A preferable addition amount is 0.0% of the entire photosensitive composition.
0.01 to 1.0% by weight, and more preferably 0.005 to 0.5%
% By weight.

In the invention according to claim 5, the compound having at least one ethylenically unsaturated double bond capable of addition polymerization (hereinafter abbreviated as “ethylenic compound”) is, for example, an unsaturated carboxylic acid, Esters of saturated carboxylic acids and aliphatic polyhydroxy compounds, esters of unsaturated carboxylic acids and aromatic polyhydroxy compounds, unsaturated carboxylic acids and polyvalent carboxylic acids and the above-mentioned aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds And the like, which can be obtained by an esterification reaction with a polyvalent hydroxy compound such as, for example, JP-A-59-7104.
No. 8 diethylene glycol di (meth) acrylate, triethylene glycol di (meth)
Acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol triacrylate,
Hydroquinone di (meth) acrylate, pyrogallol triacrylate, 2,2'-bis (4-acryloxydiethoxyphenyl) propane and the like can be mentioned. Others
Examples thereof include (meth) acrylamides such as ethylenebis (meth) acrylamide and hexamethylenebis (meth) acrylamide, and vinyl urethane compounds and epoxy (meth) acrylate. Component A is used in an amount of usually 5 to 70% by weight, preferably 10 to 50% by weight, based on the total solid content of the photosensitive composition.

In the invention according to the fifth aspect, the alkali-soluble or swellable acidic vinyl copolymer containing a compound having an aromatic hydroxyl group in a side chain as a constituent unit in the molecule is preferably an aromatic vinyl compound. Vinyl monomers having a hydroxyl group in a side chain, specifically, o, m, p-hydroxyphenyl (meth) acrylamide, o, m, p-hydroxystyrene, o, m, p-hydroxyphenyl (meth) acrylate, It can be obtained by copolymerizing o, m, p-hydroxyphenylmaleimide and the like with vinyl monomers shown in the following (a) to (j).

The alkali-soluble or swellable acidic vinyl copolymer containing a compound containing an aliphatic hydroxyl group in the side chain as a constitutional unit in the molecule is a vinyl copolymer having an aliphatic hydroxyl group in the side chain. It can be obtained by copolymerizing a monomer, for example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate and the like with a vinyl monomer shown in the following (a) to (j).

(A) α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic anhydride and itaconic acid;
(B) Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, acrylic acid-
(Substituted) alkyl acrylates such as 2-chloroethyl, glycidyl acrylate and N-dimethylaminoethyl acrylate, (c) methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, cyclohexyl methacrylate, 4-hydroxybutyl methacrylate, glycidyl methacrylate (Substituted) alkyl methacrylates such as N-dimethylaminoethyl methacrylate,
(D) acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N-ethylacrylamide, N-hexylmethacrylamide, N-hydroxyethylacrylamide, N-
Acrylamide or methacrylamides such as phenylacrylamide, N-nitrophenylacrylamide, N-ethyl-N-phenylacrylamide, (e) ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether; Vinyl ethers such as phenyl vinyl ether,
(F) vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate, and vinyl benzoate; (g) styrenes such as styrene, α-methyl styrene, methyl styrene, and chloromethyl styrene; and (h) methyl vinyl ketone , Ethyl ketone, propyl vinyl ketone, vinyl ketones such as phenyl vinyl ketone,
(I) olefins such as ethylene, propylene, isobutylene, butadiene, isoprene, (j) N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine, acrylonitrile, methacrylonitrile, and the like.
Other monomers that can be copolymerized with the above monomers may be copolymerized. Acidic vinyl copolymer in the present invention,
It is preferable from the viewpoint of developability that the unsaturated carboxylic acid mentioned as (a) is contained, a preferable acid value is 10 to 100, and a preferable molecular weight is 30,000 to 130,000.

The acidic vinyl copolymer used in the present invention usually contains 30 to 99% by weight in the solid component of the photosensitive composition.
Preferably, the content is 40 to 95% by weight.

In the invention according to claim 5, the photopolymerization initiator is not particularly limited, and a conventionally known photopolymerization initiator can be used, for example, benzoin, benzoin alkyl ether,
Benzophenone, anthraquinone, Michler's ketone,
Any of a trihalomethyl-s-triazine compound, an oxadiazole compound, a complex system of biimidazole and Michler's ketone, a complex system of thioxanthone and an aromatic tertiary amine, and the like can be suitably used.

The amount of the photopolymerization initiator used in the invention according to claim 5 is usually 0.5 to 0.5 in the solid component of the photosensitive composition.
The content is preferably 30% by weight, more preferably 2 to 10% by weight.

Examples of the diazo resin contained in the photosensitive composition in the invention according to claim 5 include, for example, condensation resins of an aromatic diazonium compound and a carbonyl compound, and salts of the condensation resins. These condensation resins, -COOH in the molecule, -OH, those obtained by introducing a substituent that imparts alkali solubility such as -S0 ₃ H preferred.
A preferred diazo resin for use in the present invention is a co-condensation compound containing an aromatic compound having at least one of the group consisting of a carboxyl group and a hydroxyl group and an aromatic diazonium compound as constituent units in the molecule. Specifically, Japanese Patent Application No. 6-33740, Japanese Patent Application Laid-Open No. 8-160
No. 612 is mentioned. The diazo resin used in the present invention usually contains 1
-20% by weight, preferably 2-10% by weight.

In the invention according to claim 5, the photosensitive composition contains a sensitizing agent for improving the lipophilicity of an image (styrene-maleic anhydride copolymer described in JP-A-55-527). Half-esterified compound by coalescing alcohol,
Novolak resins, 50% fatty acid esters of p-hydroxystyrene, etc.). Furthermore, plasticizers for imparting flexibility and abrasion resistance of the coating film (butylphthalyl, polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, tributyl phosphate,
Trioctyl phosphate, tetrahydrofurfuryl oleate, oligomers and polymers of acrylic acid or methacrylic acid, particularly preferably tricresyl phosphate) are added. In the photosensitive composition, phosphoric acid, phosphorous acid, citric acid, oxalic acid, dipicophosphoric acid, benzenesulfonic acid, naphthalenesulfonic acid, sulfosalicylic acid, 4-methoxy-2-hydroxybenzophenone are used in order to extend the stability over time. −
5-sulfonic acid, tartaric acid and the like are added.

Further, in the photosensitive composition, a printing-out agent for obtaining a visible image immediately after exposure, and a dye such as a dye or a pigment as an image coloring agent can be added. As the coloring matter, those which change color by reacting with free radicals or acids are preferable. Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.), Oil Yellow # 101, Oil Yellow # 103, Oil Pink # 312, Oil Red, Oil Green BG, Oil Blue BOS, Oil Blue #
603, oil black BY, oil black BS, oil black T-505 (all manufactured by Orient Chemical Industry Co., Ltd.), patent pure blue (manufactured by Sumitomo Sangoku Chemical), crystal violet (CI42555), methyl violet (CI42535), Ethyl violet, rhodamine B (CI145170B), malachite green (CI42000), methylene blue (CI
52015), brilliant blue, methyl green,
Erythricin B, basic fuchsin, m-cresol purple, auramine, 4-p-diethylaminophenyliminaphthoquinone, triphenylmethane series represented by cyano-p-diethylaminophenylacetanilide, diphenylmethane series, oxazine series, xanthene series, iminonaphthoquinone Examples of the color, azomethine-based or anthraquinone-based dyes changing from colored to colorless or different colored tones.

On the other hand, examples of the color changing agent which changes from colorless to colored include leuco dye, triphenylamine, diphenylamine, o-chloroaniline, 1,2,3-triphenylguanidine, naphthylamine, diaminodiphenylmethane, p, p '. -Bis-dimethylaminodiphenylamine, 1,2-dianilinoethylene, p, p ', p "-
Tris-dimethylaminotriphenylmethane, p, p '
-Bis-dimethylaminodiphenylmethylimine, p,
p ', p "-triamino-o-methyltriphenylmethane, p, p'-bis-dimethylaminodiphenyl-4-
Primary or secondary arylamine dyes represented by anilinonaphthylmethane and p, p ', p "-triaminotriphenylmethane. Preferred are triphenylmethane dyes and diphenylmethane dyes. More preferred are triphenylmethane dyes, especially Victoria Pure Blue BOH, which are contained in the photosensitive composition at about 0.5 to 10% by weight, preferably 1 to 5% by weight.

In the photosensitive composition, cyclic acid anhydrides, phenols, organic acids and higher alcohols can be added in order to enhance developability. The photosensitive composition dissolves each of the above components, for example, as described in JP-A-62-251739.
In a solvent as described in (1), at a solid content of 2 to 50% by weight, and dissolved and dispersed, and 0.3 to 4.
It is coated on a support at 0 g / m ² and dried. A surfactant can be added to the photosensitive composition as in the case of the positive type composition.

In the invention according to claim 6 or 7, examples of the acid generator include various known compounds and mixtures. Such as diazonium, phosphonium, sulfonium or iodonium _{BF 4 -, PF 6 -,} SbF
^{_{6 -, SiF 6 2 -,}} ClO 4 - salt such as, JP-A-4-42
No. 158, an alkylonium salt, an organic halogen compound, an orthoquinone-diazidosulfonyl chloride, and an organometallic / organohalogen compound are also actinic ray-sensitive components that form or separate an acid upon irradiation with actinic light. It can be used as an acid generator in the invention. In principle, all organic halogen compounds which are known as free-radical-forming photoinitiators are compounds which form hydrohalic acids and can be used as acid generators in the present invention.

Examples of the compounds forming the above-mentioned hydrohalic acid include US Pat. Nos. 3,515,552, 3,536,489 and 3,779,778, and West German Patent Publication. The compounds described in U.S. Pat. No. 2,243,621 can be used, and for example, compounds capable of generating an acid by photolysis described in West German Patent Publication No. 2,610,842 can also be used. Also, o-naphthoquinonediazide-4-sulfonic acid halogenide described in JP-A-50-36209,
No. 134410, an acid generator capable of forming an acid polymer by ultraviolet rays, for example, a compound having two oxysulfonyl groups and two oxycarbonyl groups, and an acid generator described in JP-A-4-19666. Specifically, tetrakis-
Aryl halides such as 1,2,4,5- (polyhalomethyl) benzene, tris (polyhalomethyl) benzene,
The polymer sulfonium salt containing silyl ether and the alkyl halide disclosed in JP-A-6-342209 are disclosed in JP-A-9-342209.
Oxime sulfonate compounds of JP-A-96900 and JP-A-6-67433, halogenated sulfolane derivatives of JP-A-4-338557, JP-A-6-236024, JP-A-6-214391, JP-A-6-214392,
Sulfonic esters of N-hydroxyimide compounds, diazo compounds or diazo resins described in JP-A-7-244378 can be used. The acid generator used in the present invention preferably has no absorption of 400 nm or more. The use of an organic halogen compound as the acid generator used in the invention according to claim 6 or 7 enables sensitivity and image formation in image formation by infrared exposure. It is preferable from the viewpoint of storage stability when used as a forming material. As the organic halogen compound, a triazine having a halogen-substituted alkyl group and an oxadiazole having a halogen-substituted alkyl group are preferable, and an s-triazine having a halogen-substituted alkyl group is particularly preferable. Specific examples of oxadiazoles having a halogen-substituted alkyl group are disclosed in
No. 74728, JP-A-55-24113, JP-A-55-24113
-77742, JP-A-60-3626 and JP-A-6
2-halomethyl-1,3,0-138,539
4-oxadiazole compound and JP-A-4-4634
The oxadiazole-based compound described in No. 4 is exemplified.
Preferred examples of the 2-halomethyl-1,3,4-oxadiazole-based photoacid generator are shown below.

In the invention according to claim 6 or 7, an organic halogen compound and a diphenyliodonium salt are used as an acid generator in view of sensitivity in image formation by infrared exposure and storage stability when used as an image forming material. preferable. As the organic halogen compound, s-triazines having a halogen-substituted alkyl group are particularly preferred. The maximum absorption wavelength λmax of the acid generator is 200 to 350.
nm, and the molar extinction coefficient ε at λmax is 1
It is preferably at least 10,000, particularly preferably at least 20,000.

Next, representative examples of the oxadiazole-based photoacid generator will be described.

[0095]

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S- having the halogen-substituted alkyl group
As the triazine, a compound represented by the following general formula (3) is preferable.

[0097]

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In the general formula (3), R represents an alkyl group,
A halogen-substituted alkyl group, a phenylvinylene group or an aryl group (for example, a phenyl group, a naphthyl group or the like) which may be substituted with an alkoxy group, or a substituted product thereof;
X ₃ represents a halogen atom.

Examples of compounds of the s-triazine photoacid generator represented by the general formula (3) are shown below.

[0100]

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[0101]

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The s-triazine acid generator is also disclosed in
44737, JP-A-9-90633, and JP-A-4
Those specifically described in JP-A-226454 can also be used.

In the invention according to claim 6 or 7, the acid generator preferably corresponds to any one of the following 1 to 3.

1. 1. having an alkali-soluble site; 2. a bromomethylaryl ketone derivative; It is a trichloroacetylamino group-containing aromatic compound.

Examples of the compound having an alkali-soluble moiety include an ester comprising a combination selected from the following description, a compound having two or more hydroxyl groups and an alkylsulfonic acid, a compound having two or more phenolic hydroxyl groups and an alkylsulfonic acid, An anthracene derivative having two or more hydroxyl groups and a sulfonic acid can be given.

Examples of the acid generator comprising an ester of a compound having two or more hydroxyl groups and an alkyl sulfonic acid include alcoholic hydroxyl groups such as ethylene glycol, propylene glycol, glycerin, and 1,2,4-butanetriol; And esters with The alkyl group of this alkyl sulfonic acid is C _n H _{2n + 1}
And those in the range of n = 1 to 4 are effective.
It is also effective to substitute a part or all of the hydrogen in the alkyl group with a halogen having a high electronegativity such as fluorine or chlorine. The alkyl sulfonic acid ester used for the acid generator does not need to convert all the hydroxyl groups of the compound containing two or more alcoholic hydroxyl groups into esters, and the hydroxyl groups may be left. By doing so, it is possible to control the solubility in an alkaline aqueous solution.

Examples of the acid generator comprising an ester of a compound having two or more phenolic hydroxyl groups and an alkyl sulfonic acid include catechol, resorcin, hydroquinone, pyrogallol, oxyhydroquinone, phloroglucin, trihydrobenzophenone, tetrahydrobenzophenone, and gallic acid. An ester of a phenolic hydroxyl group such as an ester with an alkyl sulfonic acid is exemplified. The alkyl group of the alkylsulfonic acid is the same as described above. The alkyl sulfonic acid ester used for the acid generator does not need to convert all the hydroxyl groups of the compound containing two or more alcoholic hydroxyl groups into esters, and the hydroxyl groups may be left. By doing so, it is possible to control the solubility in an alkaline aqueous solution.

Examples of the acid generator consisting of an ester of an anthracene derivative having two or more hydroxyl groups and a sulfonic acid include esters of a hydroxyl group of a dihydroxyanthracene, a trihydroxyanthracene and an ester of a sulfonic acid. As the sulfonic acid, alkyl sulfonic acid, aryl sulfonic acid,
1,2-naphthoquinonediazidosulfonic acid is exemplified. The alkyl of the alkyl sulfonic acid is the same as described above. The sulfonic acid ester used for the photoacid generator does not need to convert all of the hydroxyl groups of the compound containing two or more hydroxyl groups into esters, and the hydroxyl groups may be left. By doing so, it is possible to control the solubility in an alkaline aqueous solution.

As the bromomethylarylketone derivative, bromomethylarylketone or dibromomethylarylketone is preferable. For example, 2-bromoacetylnaphthalene, 2-bromoacetyl-6,7-dimethoxynaphthalene, 2-bromoacetylnaphthalene, 2-dibromoacetyl-6,7-dimethoxynaphthalene, 1-
Hydroxy-4-bromo-2-bromoacetylnaphthalene, 1-hydroxy-4-bromo-2-dibromoacetylnaphthalene, 2-hydroxy-1-bromoacetylnaphthalene, 1,4-bis (bromoacetyl) benzene,
4,4'-bis (bromoacetyl) biphenyl, 1,
3,5-tris (bromoacetyl) benzene, 1,3
5-tris (dibromoacetyl) benzene and the like, and these can be used alone or in combination of two or more.

Further, as the trichloroacetylamino group-containing aromatic compound, those having the following structures are more preferable.

[0111]

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In the formula, R _{1 to} R ₅ represent hydrogen, an alkyl or alkoxy group having 4 or less carbon atoms, a halogen atom, a phenylamino group, a phenoxy group, a benzyl group, a benzoyl group, an acetyl group, and a trichloroacetylamino group. , R _1-
R ₅ may be the same or different. Specifically, for example, 4-phenoxytrichloroacetanilide,
4-methoxytrichloroacetanilide, 2,3-dimethoxytrichloroacetanilide, 4-methoxy-2-
Chlorotrichloroacetanilide, 3-acetyltrichloroacetanilide, 4-phenyltrichloroacetanilide, 2,3,4-trifluorotrichloroacetanilide, 2,4,5-trimethyltrichloroacetanilide, 2,4,6-tribromotrichloroacetanilide, 2, 4,6-trimethyltrichloroacetanilide, 2,4-dichlorotrichloroacetanilide, 2,
4, -dimethoxytrichloroacetanilide, 2,5-
Dichlorotrichloroacetanilide, 2,5-dimethoxytrichloroacetanilide, 2,6-dimethyltrichloroacetanilide, 2-ethyltrichloroacetanilide, 2-fluorotrichloroacetanilide, 2-methyltrichloroacetanilide, 2-methyl-6-ethyltrichloroacetanilide, 2- Phenoxyacetanilide, 2-propyltrichloroacetanilide, 3,
4-dichlorotrichloroacetanilide, 3,4-dimethoxytrichloroacetanilide, 3,4-dimethyltrichloroacetanilide, 4-butylacetanilide,
4-ethylacetanilide, 4-fluoroacetanilide, 4-iodoacetanilide, 4-propylacetanilide, 2,3,4,5,6-pentafluoroacetanilide, 4-propoxyacetanilide, 4-acetylacetanilide and the like, In particular, they have high thermal stability and can be suitable photoacid generators.

In the present invention, the photoacid generators can be used alone or in combination of two or more. The content thereof can be varied widely depending on its chemical properties and the photosensitive composition or its physical properties. The range of about 0.1 to about 20% by weight, and preferably 0.2 to 10% by weight, based on the total weight of the solid content of the photosensitive layer when the composition is in a dry state or as an image forming material is suitable. Range.

The acid-decomposable compound of the invention according to claim 6 includes JP-A-48-89003 and JP-A-5-12071.
No. 4, No. 53-133429, No. 55-12995
Compounds having a C--O--C bond described in JP-A Nos. 55-126236 and 56-17345, and Si-O- compounds described in JP-A Nos. 60-37549 and 60-112446. Compound having C bond, JP-A-60
And other acid-decomposable compounds described in JP-A-6-3225 and JP-A-60-10247. Further, compounds having a Si-N bond described in JP-A-62-222246, Carbonates described in JP-A-251743, orthotitanates described in JP-A-62-280841, and JP-A-62-2
Orthosilicate described in No. 80842,
Acetals and ketals described in JP-A-63-10153, compounds having a CS bond described in JP-A-62-244038, 63-23144
A compound having a -OC (= O)-bond of No. 2 can be used.

Of the above, acetal and silyl ether are preferred.

The acid-decomposable compound is preferably a compound which is decomposed by the action of an acid to form a diol compound containing an ethylene glycol component or a propylene glycol component. Examples of such diol compounds include:
General formula-(CH ₂ -CH ₂ -O) _n- or-(CH ₂ -C
Those containing a component represented by H ₂ (CH ₃ ) —O) _m — are preferred. Here, n or m is preferably in the range of 1 to 5. The _{- (CH 2 -CH 2 -O)} n - (CH 2 -CH 2 (CH 3)
Those containing a copolymer component represented by —O) _m — are also preferable. Examples of these diol compounds include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, pentapropylene glycol, polypropylene glycol, A poly-ethylene glycol-propylene glycol copolymer is exemplified. Ethylene glycol and diethylene glycol are particularly preferred from the viewpoint of sensitivity and development stability. Further, acetal or silyl ether containing these diol components is particularly preferable, and is a polycondensation compound represented by the general formula (4).

[0117] Formula _{(4) R 1 - (XR} 2 R 3 -O-R 4) n - (XR 5 R 6 -O-R 7 -
O) _m -R _{8 In the} general formula (4), n represents an integer of 1 or more, and m represents an integer including 0. X represents a C atom or a Si atom; R ₄ represents an ethyleneoxy group or a propyleneoxy group, which corresponds to the diol compound containing an ethylene glycol component or a propylene glycol component defined in claim 1.
R ₂ and R ₅ represent a hydrogen atom, an alkyl group or an aryl group;
₃ , R ₆ represent an alkyl group or an aryl group, and R ₂ and R ₃ or R ₅ and R ₆ may be bonded to each other to form a substituted or unsubstituted ring. R ₇ represents an alkylene group. R ₁ is a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an alkyleneoxy group, a halogen atom, and R ₈ is a hydrogen atom or -X
R ₂ indicates an R ₃ R _1, or -XR ₅ R ₆ R _1.

The acetal is preferably synthesized from the condensation of the diol compound with the dimethyl acetal or diethyl acetal of aldehyde or ketone in view of the yield. Examples of such aldehydes include acetaldehyde, chloral, ethoxyacetaldehyde, benzyloxyacetaldehyde, phenylacetaldehyde, diphenylacetaldehyde, phenoxyacetaldehyde, propionaldehyde, 2-phenyl and 3-phenylacetaldehyde.
-Phenylaldehyde, isobutoxybivalinaldehyde, benzyloxybivalinaldehyde, 3-ethoxypropanal, 3-cyano-propanal, n-butanal, isobutanal, 3-chloro-butanal, 3-chlorobutanal
Methoxy-butanal, 2,2-dimethyl-4-cyano-butanal, 2- and 3-ethylbutanal, n-pentanal, 2- and 3-methyl-pentanal, 2-
Bromo-3-methyl-pentanal, n-hexanal, cyclopentanecarbaldehyde, n-heptanal, cyclohexanecarbaldehyde, 1,2,3,6-
Tetrahydro-benzaldehyde, 3-ethylpentanal, 3- and 4-methyl-hexanal, n-octanal, 2- and 4-ethyl-hexanal, 3,5
5-trimethylhexanal, 4-methylheptanal, 3-ethyl-n-heptanal, decanal, dodecanal, crotonaldehyde, benzaldehyde, 2
-, 3- and 4-bromobenzaldehyde, 2,4- and 3,4-chloro-benzaldehyde, 4-methoxy-
Benzaldehyde, 2,3- and 2,4-dimethoxy-
Benzaldehyde, 2-, 3- and 4-fluoro-benzaldehyde, 2,3- and 4-methylbenzaldehyde, 4-isopropyl-benzaldehyde, 3- and 4
-Tetrafluoroethoxy-benzaldehyde, 1- and 2-naphthaldehyde, furfural, thiophene-
Examples thereof include 2-aldehyde, terephthalaldehyde, piperonal, 2-pyridinecarbaldehyde, p-hydroxy-benzaldehyde, 3,4-dihydroxy-benzaldehyde, 5-methyl-furaldehyde, vanillin and the like. As ketones, phenylacetone, 1,
3-diphenylacetone, 2,2-diphenylacetone, chloro- and bromo-acetone, benzylacetone, methylethylketone, benzyl-propylketone,
Ethyl benzyl ketone, benzyl methyl ketone, isobutyl ketone, 5-methyl-hexane-2-one, 2-methyl-pentan-2-one, 2-methyl-pentane-3
-One, hexane-2-one, pentan-3-one, 2
-Methyl-butan-3-one, 2,2-dimethyl-butan-3-one, 5-methyl-heptane-3-one, octane-2-one, octane-3-one, octane-3-one
ON, nonan-2-one, nonan-3-one, nonane-
5-one, hept-2-one, heptan-3-one,
Heptane-4-one, undecane-2-one, undecane-4-one, undecane-5-one, undecane-6
-One, dodecane-2-one, dodecane-3-one, tridecane-2-one, tridecane-3-one, tridecan-7-one, dinonyl ketone, dioctyl ketone, 2
-Methyl-octane-3-one, cyclopropylmethylketone, decane-2-one, decane-3-one, decane-4-one, methyl-α-naphthyl-ketone, didecylketone, diheptylketone, dihexylketone, acetophenone , 4-methoxy-acetophenone, 4-chloro-acetophenone, 2,4-dimethyl-acetophenone, 2-, 3- and 4-fluoroacetophenone,
-, 3- and 4-methylacetophenone, 2-, 3- and 4-methoxyacetophenone, propiophenone,
-Methoxy-propiophenone, butyrophenone, valerophenone, benzophenone, 3,4-dihydroxybenzophenone, 2,5-dimethoxybenzophenone,
3,4-dimethoxybenzophenone, 3,4-dimethylbenzophenone, cyclohexanone, 2-phenyl-cyclohexanone, 2-, 3- and 4-methyl-cyclohexanone, 4-t-butyl-cyclohexanone, 2,6
-Dimethylcyclohexanone, 2-chlorocyclohexanone, cyclopentanone, cycloheptanone, cyclooctanone, cyclononanone, 2-cyclohexene-1one, cyclohexylpropanone, flavanone, cyclohexane-1,4-dione, cyclohexane-1,3- Diontropone, isophorone and the like.

Particularly preferred are aldehyde or ketone components having a solubility in water at 25 ° C. of 1 to 100 g / l. If the amount is less than 1 g / l, sludge is likely to be generated in the continuous processing, and if it is more than 100 g / l, the resolution of the formed image tends to decrease. Specific examples include benzaldehyde, 4-hydroxybenzaldehyde, 3,4
-Dihydroxybenzaldehyde, 2-pyridinecarbaldehyde, piperonal, furaldehyde, terephthalaldehyde, 5-methyl-2-furaldehyde, phenoxyacetaldehyde, phenylacetaldehyde, cyclohexanecarbaldehyde, vanillin, cyclohexanone, cyclohexen-1one, isobutyraldehyde, pentanal And the like. Of these, cyclohexanone is the most stable and preferred in continuous processing.

Silyl ethers are synthesized by condensation of a silyl compound with the diol compound. Specific examples of the silyl compound include dichlorodimethylsilane, dichlorodiethylsilane, methylphenyldichlorosilane, diphenyldichlorosilane, and methylbenzyldichlorosilane. The solubility of the silyl compound formed by decomposition under the action of an acid in water at 25 ° C. is 1 to 100 g / l.
Are preferred.

Acetals and silyl ethers may be co-condensed with other alcohol components in addition to the above-mentioned diol compounds. Specific examples of the alcohol component include substituted or unsubstituted monoalkyl alcohols such as methanol, ethanol, n-propanol, isopropanol, butanol, pentanol, hexanol, cyclohexanol, and benzyl alcohol; ethylene glycol monomethyl ether; Examples thereof include glycol ether alcohols such as ethyl ether, ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monophenyl ether, and substituted or unsubstituted polyethylene glycol alkyl ethers and polyethylene glycol phenyl ethers. Further, as the dihydric alcohol, for example, pentane-1,5-diol, n-hexane-
1,6-diol, 2-ethylhexane-1,6-diol, 2,3-dimethyl-hexane-1,6-diol, heptane-1,7-diol, cyclohexane-
1,4-diol, nonane-1,7-diol, nonane-1,9-diol, 3,6-dimethyl-nonane-1,
9-diol, decane-1,10-diol, dodecane-1,12-diol, 1,4-bis- (hydroxymethyl) -cyclohexane, 2-ethyl-1,4-bis-
(Hydroxymethyl) -cyclohexane, 2-methyl-
Cyclohexane-1,4-diethanol, 2-methyl-
Cyclohexane-1,4-dipropanol, thio-dipropylene glycol, 3-methylpentane-1,5-diol, dibutylene-glycol, 4,8-bis- (hydroxymethyl) -tricyclodecane, 2-butene-
1,4-diol, p-xylylene glycol, 2,5
-Dimethyl-hex-3-yne-2,5-diol, bis- (2-hydroxyethyl) -sulfide, 2,
2,4,4, -tetramethylcyclobutane-1,3-diol and the like. In this embodiment, the molar ratio of the diol compound defined in claim 1 to the other alcohol component is preferably 70/30 to 100/0, and 85/15 to 100.
100/0 is more preferred.

The preferred molecular weight range of the above-mentioned acetal or silyl ether containing a diol component is GPC
Weight average molecular weight M measured in terms of polystyrene
w is 500 to 10000, preferably 1000 to 300
0.

In the invention according to claim 6, the preferable content of the acid-decomposable compound in the layer of the photosensitive composition is 5
-50%, more preferably 10-30%. Above this level, the sensitivity decreases, and below this level, the image forming ability decreases.

As the infrared absorber used in the invention according to claim 6 or 7, a compound absorbing light having a wavelength of 700 to 1500 nm is used. For example, wavelength 700 nm
It is preferable to use an infrared absorbing dye having the above absorption, carbon black, magnetic powder, and the like. Particularly preferred infrared absorbing dyes are dyes having a maximum absorption at 700 to 1200 nm and a peak molar extinction coefficient ε of 105 or more.

Examples of the infrared absorbing dye include a cyanine dye, a squarium dye, a croconium dye, an azurenium dye, a phthalocyanine dye, a naphthalocyanine dye, a polymethine dye, a naphthoquinone dye,
Thiopyrylium dyes, dithiol metal complex dyes, anthraquinone dyes, indoaniline metal complex dyes,
And intermolecular CT dyes. Examples of the infrared absorbing dye include JP-A-63-139191 and JP-A-64-335.
No. 47, JP-A-1-160683 and 1-28075
No. 0, No. 1-293342, No. 2-2074, No. 3
-26593, 3-30991 and 3-3489
No. 1, 3-36093, 3-36094, 3
No.-36095, No. 3-42281, No. 3-1034
No. 76 and the like.

In the invention according to claim 6 or 7, a cyanine dye represented by the following general formula (5) or (6) is particularly preferred as the infrared absorber.

[0127]

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In the general formulas (5) and (6), Z ₁ and Z ₂ each represent a sulfur atom, a selenium atom or an oxygen atom, and X ₁ and X ₂ each represent a benzocondensation which may have a substituent. Represents a group of nonmetallic atoms necessary for forming a ring or a naphtho condensed ring, R ₃ and R ₄ each represent a substituent, and one of R ₃ and R ₄ has an anionic dissociable group.
R ₅ , R ₆ , R ₇ and R ₈ each represent an alkyl group having 1 to 3 carbon atoms, a hydrogen atom or a halogen atom. L represents a chain of conjugated bonds having 5 to 13 carbon atoms.

The cyanine dyes represented by formula (5) or (6) include those which form a cation and have a counter anion. In this case, the counter anion is C
_{^{l -, Br -, ClO 4}} -, BF 4 -, include alkylboron arsenide of t- butyl triphenyl borate arsenide.

In the general formulas (5) and (6), the number of carbon atoms (n) in the conjugated bond chain represented by L is determined by using a laser which emits infrared rays as a light source for image exposure. It is preferable to select an effective value according to the transmission wavelength of the light. For example, Y at an emission wavelength of 1060 nm
When an AG laser is used, n is preferably 9 to 13. The conjugate bond may have any substituent, and the conjugate bond may form a ring with a plurality of substituents. Further, the ring represented by X ₁ and the ring represented by X ₂ can have an arbitrary substituent. The halogen atom as a substituent, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, -SO ₃ M and -CO
A group selected from OM (M is a hydrogen atom or an alkali metal atom) is preferable. R ₃ and R ₄ are each an arbitrary substituent, preferably an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms;-((CH ₂ ) n-
_{O-) k- (CH 2) mOR} (n and m are each an integer of 1 to 3, k is 0 or 1, R represents an alkyl group having 1 to 5 carbon atoms);. R ₃ and R ₄ One of —R—SO ₃ M and the other —R—SO ₃ — (R represents an alkyl group having 1 to 5 carbon atoms, M represents an alkali metal atom); or one of R ₃ and R ₄ represents —R In -COOM, the other is -R-COO- (R represents an alkyl group having 1 to 5 carbon atoms, and M represents an alkali metal atom). R ₃ and R ₄ are, in terms of sensitivity and developability, R ₃ and one is above R ₄ -R-SO ₃ ^- or -R-C
OO ⁻ , and the other is preferably —R—SO ₃ M or —R-COOM.

The infrared absorbing dye is 750 to 900 nm when a semiconductor laser is used as a light source for image exposure,
900 to 1200 nm when using a YAG laser
And those having a molar extinction coefficient of ε> 1 × 10 ⁵ are preferred. Further, one or more dyes belonging to both systems may be used in combination.

Representative specific examples of the infrared absorber preferably used in the invention according to claim 6 or 7 are shown below.
It is not limited to these.

[0133]

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[0134]

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[0135]

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[0136]

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[0137]

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[0138]

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[0139]

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[0140]

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[0141]

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[0142]

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[0143]

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[0144]

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[0145]

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[0146]

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These dyes can be synthesized by known methods, but the following commercially available products can also be used.

Nippon Kayaku: IR750 (anthraquinone type); IR002, IR003 (aluminum type);
R820 (polymethine type); IRG022, IRG03
3 (diimmonium-based); CY-2, CY-4, CY-
9, CY-20, Mitsui Toatsu: KIR103, SIR10
3 (phthalocyanine); KIR101, SIR114
(Anthraquinone type); PA1001, PA1005
PA1006, SIR128 (metal complex type), Dainippon Ink & Chemicals: Fastogen blue 8120, Midori Kagaku: MIR-101, 1011, 1021 and the like. In addition, it is also commercially available from various companies such as Nippon Kogaku Dye, Sumitomo Chemical, Fuji Photo Film and the like.

In the present invention, the amount of the infrared absorber added is preferably in the range of 0.5 to 10% by weight. If the amount exceeds 10% by weight, the developability of the non-image area (exposed area) decreases, and if it is less than 0.5% by weight, the sensitivity decreases.

The photosensitive composition of the invention according to claim 6 can significantly improve the printing durability when used as a lithographic printing plate by having a pigment. Examples of the pigment include known organic and inorganic pigments, and the pigments described in “Coloring Material Engineering Handbook” by Asakura Shoten and “Pigment Handbook” by Seibundo Shinkosha can be used without any particular limitation. Further, in order to obtain a visible image after development, the pigment is preferably colored,
More preferably, a high concentration is obtained. In that respect, it is preferable that the pigment is selected from phthalocyanine and carbon black not only to improve the printing durability but also to obtain a visible image after development.

In the invention according to claim 7, the photoacid generator according to claim 6 can be used as the photoacid generator.

In the invention according to claim 7, the compound insolubilized with an acid includes a silanol compound, a compound containing a carboxylic acid or a carboxylic acid derivative, a compound having a hydroxyl group, a compound having a cationic double bond, and an aromatic compound. Secondary or tertiary alcohols having a group,
An alkali-soluble polymer having an aromatic ring having a methylol group, an alkoxymethyl group or an acetoxymethyl group in a molecule, an aminoplast, a compound represented by the following general formula (A), an alicyclic alcohol and / or a heterocyclic alcohol. Can be used.

The silanol compound has, on average, one or more hydroxyl groups bonded to silicon atoms per silicon atom. Here, the average means that, for example, even if a compound has one silicon atom to which no hydroxyl group is bonded, the same effect can be obtained if one silicon atom to which two hydroxyl groups are bonded is obtained. is there. As such a silanol compound, for example,
Diphenylsilanediol, triphenylsilanol,
Cis- (1,3,5,7-tetrahydroxy) -1,
3,5,7-tetraphenylcyclotetrasiloxane or the like can be used.

The amount of the silanol compound is 5 to 70% by weight.
Is preferably within the range.

Examples of the carboxylic acid or carboxylic acid derivative include aromatic carboxylic acids such as cinnamic acid, benzoic acid, tolylacetic acid, toluic acid, and isophthalic acid; aromatic esters such as dimethyl isophthalate and di-t-butyl isophthalate;
Acid anhydrides such as glutaric anhydride, succinic anhydride and benzoic anhydride, styrene-maleic anhydride copolymer, styrene
Copolymers such as methacrylic acid copolymer are exemplified.

As the compound having a hydroxyl group,
Polyhydric alcohols such as glycerin, poly p-hydroxystyrene, p-hydroxystyrene / styrene copolymer,
High molecular compounds such as novolak resins are exemplified.

The composition ratio of the carboxylic acid or its derivative to the compound having a hydroxyl group is from 1:30 to 30 in equivalent ratio.
It is preferably in the range of 1 to 1.

One of the compound having a hydroxyl group and the carboxylic acid or a derivative thereof may be a high molecular compound. When the compound having a hydroxyl group is a polymer compound, it is preferable to use a carboxylic acid or a derivative thereof in an amount of 1 to 50 in a weight ratio to the polymer compound 100. When the carboxylic acid or its derivative is a polymer compound, it is preferable to use a compound having a hydroxyl group with respect to the polymer compound 100 in an amount of 1 to 20 by weight ratio.

From the viewpoint of coatability, at least one of the carboxylic acid and the compound having a hydroxyl group is preferably a high molecular compound. However, even if both are low molecular weight, it is sufficient that the coating film can be formed by a method such as mixing a high molecular compound. As the high molecular compound, the alkali-soluble polymer according to claim 1 is preferable.

Further, a high molecular compound having both a compound having a hydroxyl group and a carboxylic acid or a carboxylic acid derivative can be used. Examples of the polymer compound include p-hydroxystyrene having a hydroxyl group and a carboxylic acid or a carboxylic acid derivative, such as methacrylic acid ester such as methyl methacrylate, acrylic acid ester such as methyl acrylate, maleic anhydride, methacrylic acid, and acrylic acid. And the like.

The weight average molecular weight of these high molecular compounds is desirably in the range of 1,000 to 50,000. If the molecular weight is less than 1,000, sufficient heat resistance and coating properties cannot be obtained. On the other hand, if the molecular weight exceeds 50,000, the solubility in an aqueous alkali solution is not sufficient, and pattern deformation due to swelling is observed, so that high resolution cannot be obtained.

The amount of the carboxylic acid or its derivative and the compound having a hydroxyl group is preferably in the range of 5 to 50% by weight.

Compounds having a cationically polymerizable double bond include p-diisopropenylbenzene, m-diisopropenylbenzene, diphenylethylene, indenone, acenaphthene, 2-norbornene, 2,5-norbornadiene, 2,3- Benzofuran, indole, 5-
Examples include at least one compound selected from the group consisting of methoxyindole, 5-methoxy-2-methylindole, N-vinyl-2-pyrrolidone, and N-vinylcarbazole.

The amount of the compound having a cationic double bond is preferably in the range of 5 to 50% by weight.

Examples of the secondary or tertiary alcohol having an aromatic group include biphenyl derivatives, naphthalene derivatives and triphenyl derivatives, and are specifically represented by the following formulas (7) to (10). Compounds.

[0166]

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In the general formulas (7) to (10), R ₁ and R ₂ may be the same or different and each represents a hydrogen atom, a methyl group or an ethyl group, and X represents a hydrogen atom, a halogen atom, a methyl A methoxy group; Y is -S
O ₂ —, —CH ₂ —, —S—, —C (CH ₃ ) ₂ —,
n represents 1 or 2.

Specific compounds include, for example, 4,4 '
-Bis (α-hydroxyisopropyl) biphenyl,
3,3'-bis (α-hydroxyisopropyl) biphenyl, 2,4,2 ', 4'-tetra (α-hydroxyisopropyl) biphenyl, 3,5,3', 5'-tetra (α-hydroxyisopropyl) Biphenyl, 4,4 '
-Bis (α-hydroxyisopropyl) biphenyl sulfone, 3,3′-bis (α-hydroxyisopropyl)
Biphenyl sulfone, 4,4'-bis (α-hydroxyisopropyl) biphenylmethane, 3,3'-bis (α
-Hydroxyisopropyl) biphenylmethane, 4,
4'-bis (α-hydroxyisopropyl) biphenyl sulfide, 3,3'-bis (α-hydroxyisopropyl) biphenyl sulfide, 2,2-bis (4-α-
Hydroxyisopropylphenyl) propane, 2,2-
And bis (3-α-hydroxyisopropylphenyl) propane. The naphthalene derivative is 1,5-bis (1
-Hydroxypropyl) naphthalene, 2,6-bis (α
-Hydroxypropyl) naphthalene and the like. Triphenyl derivatives include tris (4-α-hydroxyisopropylphenyl) methane, tris (3-α-hydroxyisopropylphenyl) methane, 1,1,1-tris (4-
α-hydroxyisopropylphenyl) ethane, 1,
1,1-tris (3-α-hydroxyisopropylphenyl) ethane and the like.

Examples of the secondary or tertiary alcohol having an aromatic group include compounds represented by the following formulas (11) to (13).

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In the general formula (11), R ₁ and R ₂ may be the same or different and each represents a hydrogen atom, a halogen atom or a methoxy group, and R ₃ represents a hydrogen atom, a phenyl group or a cyclopropyl group. .

In the general formula (12), R ₄ and R ₅ may be the same or different and each represents a hydrogen atom or a phenyl group.

In the general formula (13), A represents an alkyl group having 4 or less carbon atoms or a methylol group.

The secondary or tertiary alcohol having a hydroxyl group at the carbon directly bonded to the aromatic ring includes phenylmethanol derivatives, alicyclic alcohols having an aromatic ring, and the like.

As the phenylmethanol derivative,
For example, diphenylmethanol, 4,4'-difluorodiphenylmethanol, 4,4'-dichloro-diphenylmethanol, 4,4'-dimethyl-diphenylmethanol, 4,4'-dimethoxydiphenylmethanol, triphenylmethanol, α- (4 -Pyridyl) -benzhydrol, benzylphenylmethanol, 1,1-diphenylethanol, cyclopropyldiphenylmethanol, 1-phenylethyl alcohol, 2-phenyl-2
-Propanol, 2-phenyl-2-butanol, 1-
Phenyl-1-butanol, 2-phenyl-3-butyn-2-ol, 1-phenyl-1-propanol, 1,
2-diphenylethylene glycol, tetraphenylethylene glycol, 2,3-diphenyl-2,3-butanediol, α-naphtholbenzein, α, α′-dihydroxy-p-diisopropylbenzene, α, α′-
Dihydroxy-m-diisopropylbenzene and the like.

Examples of the alicyclic alcohol having an aromatic ring include 1-indanol, 2-bromoindanol,
Chromanol, 9-fluorenol, 9-hydroxy-
3-fluorene, 9-hydroxyxanthene, 1-acenaphthenol, 9-hydroxy-3-nitrofluorene, thiochroman-4-ol, 9-phenylxanthen-9-ol, 1,5-dihydroxy-1,2,3 ,
4-tetrahydronaphthalene, dibenzosuberenol,
Dibenzosuberol and the like.

Further, in addition to the above, 1- (9-anthryl) ethanol, 2,2,2
Examples thereof include 2-trifluoro-1- (9-anthryl) ethanol and 1-naphthylethanol.

As the alkali-soluble polymer having an aromatic ring having a methylol group, an alkoxymethyl group or an acetoxymethyl group in the molecule, one or two hydrogen atoms on the aromatic ring of the compound represented by the following general formula (14) are used. Polymers having the excluded group in the molecule are exemplified.

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In the general formula (14), X represents a methylol group, an alkoxymethyl group having 1 to 5 carbon atoms or an acetoxymethyl group. Y represents an alkyl group, a hydroxyl group, a halogen atom, a hydrogen atom, or an alkoxy group.

Further, as the alkali-soluble polymer to be contained in the photosensitive layer of the invention according to claim 5, a polymer compound having a repeating unit represented by the following general formula (15) or (16) is preferable.

[0182]

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In the general formulas (15) and (16), R
₁ represents an alkyl group, a hydrogen atom, a halogen atom or a cyano group, and L represents a single bond, -O-, -O-CO-, -CON.
R _3- , -CONR ₃ CO-, -CONR ₃ SO _2- , -N
R ₃ —, —NR ₃ CO—, —NR ₃ SO ₂ —, —SO ₂ —,
Represents —SO ₂ NR ₃ — or —SO ₂ NR ₃ CO— (R ₃ represents a hydrogen atom, an alkyl group, an aralkyl group or an aromatic ring group). X and Y have the same meanings as X and Y in formula (12).

The repeating unit represented by the above general formula (15) or (16) includes vinyl benzyl alcohol, α-methyl vinyl benzyl alcohol, vinyl benzyl acetate, α-methyl vinyl benzyl acetate, p-methoxy styrene, It is preferable to copolymerize with a monomer such as methylolphenyl methacrylamide.

The aminoplast is preferably a compound represented by the following general formula (17).

[0186]

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In the general formula (17), Z is -NRR '
Or a phenyl group. _{R, R ', R 10 ~R} 13 are each a hydrogen _{atom, -CH 2 OH, -CH 2 OR} a or -CO-OR _a
Represents R _a represents an alkyl group.

The melamine or benzoguanamine represented by the general formula (17) is easily available as a commercial product, and the methylol form thereof is obtained by condensation of melamine or benzoguanamine with formalin. Ethers can be obtained by modifying a methylol compound with various alcohols by a known method. As the alkyl group represented by _Ra in the general formula (17), an alkyl group having 1 to 4 carbon atoms which may be linear or branched is preferable.

Specific examples of the compound represented by the general formula (17) include the following, but are not limited thereto.

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[0191]

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As the aminoplast, the following general formula (1)
8) a compound represented by the following general formula (19), a melamine resin having a plurality of triazine nuclei bonded thereto through a bond represented by the following general formula (19), and a compound represented by the following general formula (20) or (21) Can also be used.

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In the general formulas (18) to (21), R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

Formula (A)

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In the general formula (A), R represents a hydrogen atom, an alkyl group having 3 or less carbon atoms, an aryl group or a tolyl group, and R ₁ , R ₂ , R ₃ and R ₄ each represent a hydrogen atom and a carbon atom. 3
Represents the following alkyl group or an alkoxy group having 3 or less carbon atoms.

Examples of the compound represented by formula (A) include o-acetylbenzoic acid, o-aldehydebenzoic acid,
o-benzoylbenzoic acid, o-toluoylbenzoic acid, o
The use of acetoxybenzoic acid is preferred.

The content of the compound represented by formula (A) in the layer of the photosensitive composition is suitably in the range of 5 to 50% by weight, preferably 10 to 30% by weight.

As the alicyclic alcohol, for example, 2
-Adamantanol, 2-methyl-2-adamantanol, 2-ethyl-2-adamantanol, 2-propyl-2-adamantanol, 2-butyl-2-adamantanol, exo-norborneol, endo-norborneol, Borneol, DL-isoborneol,
Terpinen-4-ol, S-cis-verbenol, isopinocanphenol, pinanediol and the like.

As the heterocyclic alcohol, for example, 1,
4-dioxane-2,3-diol, 5-methyl-1,
4-dioxane-2,3-diol, 5,6-dimethyl-1,4-dioxane-2,3-diol, DL-ex
o-Hydroxytropinone, 4-hydroxy-4-phenylpiperidine, 3-quinuclidinol, 4-chromanol, thiochroman-4-ol, DL-mavalonic acid lactone and the like. The heterocyclic alcohol preferably contains O or S in the heterocyclic ring.

In addition to alicyclic alcohols and heterocyclic alcohols, secondary or tertiary alcohols may be further used.

The content of the alicyclic or heterocyclic alcohol in the layer of the photosensitive composition is suitably from 5 to 50% by weight, preferably from 10 to 30% by weight.

In the invention according to claim 6 or 7, it is preferable to use, in addition to the above components, a resin soluble in alkaline water as a binder in the photosensitive composition. Specifically, phenol formaldehyde resins, o-, m- and p-cresol formaldehyde resins, m- / p-mixed cresol formaldehyde resins,
Phenol / cresol (o-, m-, p-, m- / p
Or a mixture of o- / m-) novolak resin such as mixed formaldehyde resin, phenol-modified xylene resin, polyhydroxystyrene, polyhalogenated hydroxystyrene, phenolic hydroxyl group described in JP-A-51-34711. And an acrylic resin containing the same.

Other suitable binders include copolymers having the following monomers as constituent units and having a molecular weight of 10,000 to 200,000.

(1) Acrylamides, methacrylamides, acrylates, methacrylates, hydroxystyrenes having an aromatic hydroxyl group;
(4-hydroxyphenyl) acrylamide, N- (4
-Hydroxyphenyl) methacrylamide, o-, m-
Or p-hydroxystyrene, o-, m- or p-hydroxyphenyl acrylate or methacrylate; (2) acrylates and methacrylates having an aliphatic hydroxyl group; 2-hydroxyethyl acrylate or methacrylate; (3) acryl Unsaturated carboxylic acids such as acid, methacrylic acid, maleic anhydride, and methaconic acid (4) Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, cyclohexyl acrylate, acrylic acid Octyl, phenyl acrylate, benzyl acrylate, 2-chloroethyl acrylate, 4-acrylic acid
(Substituted) acrylates such as hydroxybutyl, glycidyl acrylate, N-dimethylaminoethyl acrylate, etc. (5) Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate (Substituted) methacrylates such as octyl methacrylate, phenyl methacrylate, benzyl methacrylate, 2-chloroethyl methacrylate, 4-hydroxybutyl methacrylate, glycidyl methacrylate, N-dimethylaminoethyl methacrylate, (6) acrylamide, Methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N-ethylacrylamide, N-ethylmethacrylamide, N-hexyl Acrylamide, N- hexyl methacrylamide, N- cyclohexyl acrylamide,
N-cyclohexylmethacrylamide, N-hydroxyethylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-phenylmethacrylamide, N-benzylacrylamide, N-benzylmethacrylamide, N-nitrophenylacrylamide, N-nitrophenyl Methacrylamide, N-ethyl-N-phenylacrylamide, N-ethyl-N-
Acrylamide or methacrylamide such as phenyl methacrylamide; (7) vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, and phenyl vinyl ether; (8) vinyl acetate, vinyl chloroacetate; Vinyl esters such as vinyl butyrate and vinyl benzoate (9) Styrenes such as styrene, methyl styrene and chloromethyl styrene (10) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone and phenyl vinyl ketone ( 11) Olefins such as ethylene, propylene, isobutylene, butadiene, isoprene, etc. (12) N-vinylpyrrolidone, N-vinyl Rubazole, 4-vinylpyridine, acrylonitrile, methacrylonitrile, etc. (13) N- (o-aminosulfonylphenyl) acrylamide, N- (m-aminosulfonylphenyl) acrylamide, N- (p-aminosulfonylphenyl) acrylamide, N Acrylamides such as-[1- (3-aminosulfonyl) naphthyl] acrylamide, N- (2-aminosulfonylethyl) acrylamide;
(O-aminosulfonylphenyl) methacrylamide,
N- (m-aminosulfonylphenyl) methacrylamide, N- (p-aminosulfonylphenyl) methacrylamide, N- [1- (3-aminosulfonyl) naphthyl] methacrylamide, N- (2-aminosulfonylethyl) methacryl Methacrylamides such as amides; o-
Unsaturated sulfonamides such as acrylates such as aminosulfonylphenyl acrylate, m-aminosulfonylphenyl acrylate, p-aminosulfonylphenyl acrylate and 1- (3-aminosulfonylphenylnaphthyl) acrylate; o-aminosulfonylphenyl methacrylate And unsaturated sulphonamides such as methacrylic acid esters such as m-aminosulfonylphenyl methacrylate, p-aminosulfonylphenyl methacrylate, 1- (3-aminosulfonylphenylnaphthyl) methacrylate.

Further, a copolymer obtained by copolymerization of the above-mentioned monomers modified with glycidyl acrylate, glycidyl methacrylate or the like is also included.

These copolymers preferably contain the unsaturated carboxylic acids listed in (3), and the copolymer preferably has an acid value of 0 to 10 meq / g, more preferably 0.2 to 10 meq / g.
It is 5.0 meq / g. The preferred molecular weight of these copolymers is 10,000 to 100,000. If necessary, a polyvinyl butyral resin, a polyurethane resin, a polyamide resin, or an epoxy resin may be added to these copolymers.

The binder is used in an amount of up to 80% by weight of the photosensitive composition.

As described in US Pat. No. 4,123,279, a carbon layer such as a t-butylphenol formaldehyde resin or an octylphenol formaldehyde resin may be further provided on the layer of the photosensitive composition of the invention according to claim 6 or 7. It is preferable to use a condensate of phenol and formaldehyde each having an alkyl group of Formulas 3 to 8 as a substituent, since the oil sensitivity of the image is improved. Further, it is preferable to add a cyclic acid anhydride, a phenol, or an organic acid to the photosensitive composition in order to increase the sensitivity.

As the cyclic anhydride, US Pat. No. 4,11
Phthalic anhydride described in Patent 5,128, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3,6-oxy - [delta ⁴ - tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, maleic acid anhydride, chlorosulfonic maleic anhydride, α-phenyl maleic anhydride, succinic anhydride, pyromellitic anhydride and the like can be used.

As phenols, bisphenol A, p-nitrophenol, p-ethoxyphenol,
2,4,4'-trihydroxybenzophenone, 2,
3,4-trihydroxybenzophenone, 4-hydroxybenzophenone, 4,4 ', 4 "-trihydroxy-
Triphenylmethane, 4,4 ', 3 ", 4"-tetrahydroxy-3,5,3',5'-tetramethyltriphenylmethane and the like.

The organic acids include those described in JP-A-60-8894.
2, sulfonic acids, sulfinic acids, alkyl sulfates, phosphonic acids described in JP-A-2-96755 and the like;
Phosphoric acid esters and carboxylic acids and the like, specifically, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, p-toluenesulfinic acid, ethyl sulfate, phenylphosphonic acid, phenylphosphinic acid, phenyl phosphate, phenyl phosphate, diphenyl phosphate, Benzoic acid, isophthalic acid, adipic acid, p-toluic acid, 3,4-dimethoxybenzoic acid,
Phthalic acid, terephthalic acid, 1,4-cyclohexene-
Examples thereof include 2,2-dicarboxylic acid, erucic acid, lauric acid, n-undecanoic acid, and ascorbic acid.

The proportion of these cyclic acid anhydrides, phenols and organic acids in the photosensitive composition is 0.05 to 15%.
% By weight, preferably 0.1 to 5% by weight.

In order to increase the processing stability (development latitude) in the photosensitive composition regardless of the development conditions,
Nonionic surfactants described in JP-A-62-251740, JP-A-59-121044, JP-A-4-131
An amphoteric surfactant described in No. 49 can be added. Specific examples of the nonionic surfactant include sorbitan tristearate, sorbitan monopalmitate, sorbitan triolate, stearic acid monoglyceride,
Examples thereof include polyoxyethylene sorbitan monooleate and polyoxyethylene nonylphenyl ether. Specific examples of the amphoteric surfactant include alkyl di (aminoethyl) glycine, alkyl polyaminoethyl glycine hydrochloride, 2-alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine and N-tetradecyl-N, N- Betaine type (for example, Daiichi Kogyo Co., Ltd.)
Manufactured by Amogen K), alkyl imidazoline (manufactured by Sanyo Chemical Co., Ltd .: Levon 15) and the like. The ratio of these surfactants in the photosensitive composition is 0.05 to 15%.
% By weight, and more preferably 0.1 to 5% by weight.

Further, a printing-out agent for obtaining a visible image immediately after exposure and a dye or pigment as an image coloring agent can be added to the photosensitive composition. As a baking agent,
Combinations of compounds that release acid upon exposure (photoacid releasing agents) and organic dyes capable of forming salts, specifically, o-type compounds described in JP-A-50-36209 and JP-A-53-8128.
Combinations of naphthoquinonediazide-4-sulfonic acid halogenides with salt-forming organic dyes and JP-A-53-362
No. 23, No. 54-74728, No. 60-3626,
The combinations of the trihalomethyl compounds and the salt-forming organic dyes described in JP-A-61-143748, JP-A-61-151644, and JP-A-63-58440 can be mentioned as representatives. Trihalomethyl compounds include oxazole-based compounds and triazine-based compounds, both of which are excellent in stability over time and give clear print-out images.

As the colorant for the image, other dyes can be used in addition to the above-mentioned salt-forming organic dyes. Suitable dyes, including salt-forming organic dyes, include oil-soluble dyes and basic dyes. Specifically, Oil Yellow # 101, Oil Yellow # 103, Oil Pink # 312, Oil Green BG, Oil Blue BOS,
Oil Blue # 603, Oil Black BY, Oil Black BS, Oil Black T-505 (all manufactured by Orient Chemical Co., Ltd.), Victoria Pure Blue, Crystal Violet (CI42555), Methyl Violet (CI42535), Ethyl Violet, Rhodamine B (CI45170B), malachite green (CI42000), methylene blue (CI5201)
5) and the like. Also, JP-A-62-293
The dye described in No. 247 is particularly preferred.

The photosensitive composition dissolves each of the above components,
For example, it is dissolved and dispersed in a solvent as described in JP-A-62-251739 at a solid content of 2 to 50% by weight,
It is coated on a support at a weight of 0.3 to 4.0 g / m ² after drying and dried. In the photosensitive composition, a surfactant for improving the coating surface quality, for example, JP-A-62-17
No. 0950 can be added. A preferable addition amount is 0.0% of the entire photosensitive composition.
0.01 to 1.0% by weight, and more preferably 0.005 to 0.5%
% By weight.

It is preferable to add a nitrocellulose, a self-oxidizing compound such as metal powder, an ultraviolet absorber and the like to the layer of the photosensitive composition of the present invention.

Further, in order to improve storage stability and to suppress a decrease in reproducibility of small spots with time after exposure, the pH of the coating solution for the photosensitive composition is adjusted, and the pH is adjusted to 3.5 to 8.0, more preferably 4.0. The value is set to 6.5 or more. If the value is 3.5 or less, the above effect cannot be expected. Such a p
It is preferable to add a basic compound as an H adjuster. The basic compound is a compound capable of capturing protons, specifically, inorganic or organic ammonium salts, organic amines, amides, urea and thiourea and derivatives thereof,
Thiazoles, pyrroles, pyrimidines, piperazines, guanidines, indoles, imidazoles, imidazolines, triazoles, morpholines, piperidines, amidines, formazines, pyridines,
Schiff bases, salts of sodium or potassium with weak acids, basic nitrogen-containing resins described in JP-A-8-123030, organic basic compounds described in JP-A-9-54437, thiosulfonate compounds described in JP-A-8-212598 And heat neutralized basic compounds (sulfonyl hydrazide compounds and the like) described in JP-A-7-219217. still,
When a heat-neutralized basic compound is used, the sensitivity is greatly improved by heating after exposure and before development. Specific examples are described below.

As the amine compound, ammonium acetate,
Methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, n-
Propylamine, di-n-propylamine, tri-n-
Propylamine, isopropylamine, sec-butylamine, tert-butylamine, cyclohexylamine, benzylamine, tricyclohexylamine, tribenzylamine, octadecylbenzylamine, stearylamine, α-phenylethylamine, β-phenylethylamine, ethylenediamine, tetramethylenediamine , Hexamethylenediamine, tetramethylammonium hydroxide, aniline, methylaniline, dimethylaniline, diphenylaniline, triphenylaniline, o
-Toluidine, m-toluidine, p-toluidine, o-
Anisidine, m-anisidine, p-anisidine, o-chloroaniline, m-chloroaniline, p-chloroaniline, o-bromoaniline, m-bromoaniline, p-bromoaniline, o-nitroaniline, m-nitroaniline, p-nitroaniline, 2,4-dinitroaniline,
2,4,6-trinitroaniline, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, benzidine, p-aminobenzoic acid, sulfanilic acid, sulfanilamide, pyridine, 4-dimethylaminopyridine, piperidine, piperazine 2-benzylimidazole, 4-phenylimidazole, 2-phenyl-4-methyl-imidazole, 2-undecyl-imidazoline, 2,4,5-trifuryl-2-imidazoline,
1,2-diphenyl-4,4-dimethyl-2-imidazoline, 2-phenyl-2-imidazoline, 1,2,3-
Triphenylguanidine, 1,2-ditolylguanidine, 1,2-dicyclohexylguanidine, 1,2,3
-Tricyclohexylguanidine, guanidine trichloroacetate, N, N'-dibenzylpiperazine, 4,4 '
-Dithiomorpholine, morpholinium trichloroacetic acid,
Examples include 2-amino-benzothiazole, 2-benzoylhydrazino-benzotoazole, allyl urea, thiourea, methyl thiourea, allyl thiourea, ethylene thiourea and the like.

A specific compound of the Schiff base is represented by the following general formula (22)

[0223]

Embedded image

(Provided that R ₁ and R ₂ are a hydrocarbon group (eg, an alkyl group such as a methyl group, an isopropyl group, an octyl group, a heptadecyl group, a cycloalkyl group such as a cyclobutyl group and a cyclohexyl group, a phenyl group, a tolyl group, etc.) R ₃ is a hydrogen atom or a hydrocarbon group (R ₁ , R ₂
The same groups as mentioned above). ) In the molecule.

The compound having the above structure can be synthesized by condensation of an aldehyde or ketone with an amine.

More specifically, a condensation reaction between a polyvalent amine and a monovalent aldehyde or a monovalent ketone, a monovalent amine with a polyvalent aldehyde or a polyvalent ketone,
It can be synthesized by a polycondensation reaction between a divalent amine and a divalent aldehyde or a divalent ketone.

Examples of monovalent amines include methylamine, propylamine, n-butylamine, n-amylamine, n-heptylamine, n-octylamine and n-octylamine.
Nanonylamine, n-decylamine, n-dodecylamine, n-tridecylamine, 1-tetradecylamine,
n-pentadecylamine, 1-hexadecylamine, n
-Heptadecylamine, 1-methylbutylamine, octadecylamine, isopropylamine, tert-butylamine, sec-butylamine, tert-amylamine, isoamylamine, 1,3-dimethylbutylamine, 3,3-dimethylbutylamine, tert-octylamine, 1,2-dimethylbutylamine, 4-methylpentylamine, 1,2,2-trimethylpropylamine, 1,3-dimethylpentylamine, cyclobutylamine, cyclopentylamine, cyclohexanemethylamine, cyclohexylamine, aniline, o-toluidine, m-Toluidine, p-toluidine, m-ethylaniline, p-ethylaniline, p-butylaniline and the like. Examples of divalent amines include methine diamine, ethylene diamine, 1,3-diaminopropane,
1,2-diaminopropane, 1,2-diamino-2-methylpropane, 2,5-dimethyl-2,5-hexanediamine, 1,4-diaminobutane, 1,5-diaminopentane, 1,4-hexane Diamine, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 4,
4'-methylenebiscyclohexaneamine, 1,2-diaminocyclohexane, 1,3-cyclohexanebismethylamine, benzidine, 4-aminophenyl ether, o-tolidine, 3,3'-dimethoxybenzidine,
o-phenylenediamine, 4-methoxy-o-phenylenediamine, 2,6-diaminotoluene, m-phenylenediamine, p-phenylenediamine, 2,3-diaminonaphthalene, 1,5-diaminonaphthalene, 1,8-
And diaminonaphthalene. Examples of monovalent aldehydes include formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, 2-methylbutyraldehyde,
Ethyl butyraldehyde, valeraldehyde, isovaleraldehyde, hexanal, 2-ethylhexanal,
2,3-dimethylvaleraldehyde, octylaldehyde, cyclohexanecarboxaldehyde, cyclooctanecarboxaldehyde, phenylacetaldehyde, 2-phenylpropionaldehyde, diphenylacetaldehyde, benzaldehyde, o-tolualdehyde, m-tolualdehyde, p-tolualdehyde, o -Anisaldehyde, m-anisaldehyde, p-anisaldehyde, o-ethoxybenzaldehyde, p-ethoxybenzaldehyde, 2,4-dimethylbenzaldehyde, 2,5-dimethylbenzaldehyde, 4-biphenylcarboxaldehyde, 2-naphthaldehyde, etc. Examples of divalent aldehydes include o-phthalic dicarboxaldehyde, isophthalaldehyde,
Terephthaldicarboxaldehyde and the like. Further, examples of monovalent ketones include acetone, 2-butanone, 2-pentanone, 3-pentanone, 3-methyl-
2-pentanone, 2-hexanone, 3-hexanone, 3
-Methylhexanone, 2-heptanone, 3-heptanone, 3-methylheptanone, 2-octanone, 3-octanone, 2-nonanone, cyclobutanone, cyclopentanone, phenylacetone, benzylacetone, 1-phenyl-2- Butanone, 1,1-diphenylacetone,
Examples include 1,3-diphenylacetone, 2-phenylcyclohexanone, 2-ylidene, β-tetralone, propiophenone, o-methylacetophenone, and benzophenone. Examples of divalent ketones include 2,4-pentane Dione, 2,3-hexanedione, 2,5-hexanedione, 2,7-octanedione, 2,3-butadione, 2-methyl-1,3-cyclopentadione, 1,3
-Cyclohexanedione, 1,4-cyclohexadione, 1,3-cyclopentanedione, 3-acetyl-2
-Heptanone, 2,2,6,6-tetramethyl-3,5
-Heptadione, 2-methyl-1,3-cyclohexanedione, 5,5-dimethyl-1,3-cyclohexanedione, dibenzoylmethane, 1,4-dibenzoylbutane, p-diacetylbenzene, m-diacetylbenzene, Benzyl, 4,4'dimethoxybenzyl, 2-phenyl-1,3-indandione, 1,3-indandione, o-dibenzoylbenzene, 1,2-naphthoquinone, 1,4-naphthoquinone and the like.

The following are specific examples of Schiff bases.

[0229]

Embedded image

The basic compound can be used without any particular limitation in addition to the compounds described above as long as it can capture a proton.

These basic compounds may be used alone or in combination of two or more. The amount used is 0.0
It is preferably from 0.01 to 10% by weight, more preferably from 0.01 to 5% by weight. When the content is 0.001% by weight or less, there is no effect of improving the storage stability and suppressing a decrease in reproducibility of small spots with time after exposure, and when the content is 10% by weight or more, the sensitivity is significantly reduced.

In the measurement of the pH, the solid content of 10% was added to any organic solvent, water or a plurality of mixed solvents used for coating.
A photosensitive composition coating solution was prepared by dissolving so as to be a weight%, and a digital pH meter of Toa Denpa Kogyo KK was used as a measuring device.
After standardizing the pH meter as a measurement condition using a meter HM-30S, the measurement part of the pH meter was lowered vertically with respect to the coating solution to be measured, and the measured value when immersed in the coating solution for 2 minutes was measured. pH.

The photosensitive composition of the invention according to claim 6 or 7 is preferably subjected to image exposure using a light source having a wavelength of 400 nm or more, particularly 700 nm or more. Examples of the light source include a semiconductor laser, a He-Ne laser, a YAG laser, a carbon dioxide laser, and the like. The output is suitably 50 mW or more per laser beam, preferably 100 mW or more.

In the case of the invention according to claim 7, it is necessary to heat-treat the photosensitive lithographic printing plate after exposure and before development.
In this case, a heat treatment at 80C to 200C for 5 to 120 seconds is preferable. Also, in claim 6, a similar heat treatment may be applied.

The photosensitive lithographic printing plate after development was
By performing the burning treatment at 300 ° C. for about 20 to 200 seconds, the mechanical strength of the photosensitive layer can be significantly improved, and when used as a printing plate, the printing durability can be greatly increased.

The surface of the aluminum lithographic printing plate of the invention according to any one of claims 1 to 10 on which the photosensitive composition is provided has the above-mentioned specific projections. The method for manufacturing a support according to claim 11 or claim 12, wherein the aluminum support having the specific protrusion is described below.
Alternatively, it can be obtained by the method for producing a support according to the invention according to Item 14.

The invention according to claim 11 or 12 is characterized in that the surface of the aluminum plate is mechanically roughened or degreased, electrolytically roughened, subjected to a surface dissolution treatment with an alkali, neutralized with an acid, and treated with an acidic electrolytic solution. After electrolytic surface roughening, surface treatment with alkali, neutralization with acid, anodic oxidation treatment, and metal oxide obtained by hydrolysis and polycondensation of organic metal compound or inorganic metal compound This is a method for producing a photosensitive lithographic printing plate in which a photosensitive composition layer is provided on a support provided with a coating layer.

In the invention according to claim 11 or 12,
The mechanical surface roughening is a method of roughening a surface of a support by applying a physical force. On the other hand, the surface dissolution treatment with alkali is also called chemical roughening. Degreasing also includes cleaning with a solvent. The term “electrolytic surface roughening” refers to a method in which an alternating current is applied in an acidic electrolytic solution to electrochemically dissolve the support surface in a pit shape to roughen the surface.

[0239] In the invention according to claim 11 or 12,
The undulations or pits are formed by appropriately combining chemical surface roughening, mechanical surface roughening, and electrolytic surface roughening. Undulation or average opening diameter of 3 to 30 μm with an average roughness of 3 to 30 μm
The large pits can be formed by mechanical surface roughening (for example, brush polishing) or electrolytic surface roughening (for example, alternating current electrolysis using an electrolyte mainly containing hydrochloric acid). Next, after performing a surface dissolution treatment with an alkali, AC electrolytic surface roughening with an electrolytic solution mainly composed of nitric acid or hydrochloric acid superimposes small pits having an average opening diameter of 0.2 to 3.0 μm uniformly and densely. Can be formed.

In the method of the present invention according to the thirteenth or fourteenth aspect, the surface treatment (roughening treatment) of the aluminum plate on which the layer of the photosensitive composition is provided comprises the steps of: In the above, the acidic electrolyte of the above step is an acidic electrolyte mainly composed of hydrochloric acid and / or acetic acid.

[0241] Further, only by electrolytic roughening with an electrolytic solution mainly composed of hydrochloric acid and / or acetic acid, undulations having an average wavelength of 3 to 30 µm or large pits having an average opening diameter of 3 to 30 µm have an average opening diameter of 0.3 to 30 µm. Small pits of 2 to 3.0 μm can be superposed uniformly and densely. The method is the manufacturing method according to the twelfth or thirteenth aspect.

In the case of the electrolytic treatment according to the fourteenth aspect,
The time required for the portion where the progress of the electrolytic treatment is slow or stopped is preferably 0.6 seconds or more and 5 seconds or less.

In order that a portion where the progress of the electrolytic treatment is fast and a portion where the progress of the electrolytic treatment is slow or stops are alternately present a plurality of times, for example, in a continuous electrolytic device as shown in FIG. The electrodes can be sparsely arranged as shown in FIG. In FIG. 1, reference numeral 1 denotes an electrolytic cell, which is filled with an electrolytic solution 7. The aluminum alloy plate web 6 supported in the liquid by the support rolls 2, 3, 4, and 5 is conveyed from left to right in the drawing. Meanwhile, a current from an AC power source flows between the electrodes a to x and the aluminum alloy plate web.

Here, the portion where the progress of the electrolytic process is fast refers to the web portion facing the electrode, and the portion where the progress of the electrolytic process is slow or stops refers to the web portion where the electrode does not exist. . Even in the web portion where no electrode is present, there is a place where leakage current from the nearby electrode flows, and the electrolytic process does not stop in the entire portion, but the electrolytic process is fast in one step in one step When the amount of electricity in the electrolytic treatment is 100 C / dm ² or less on average, a uniform grain can be obtained.

Also, as shown in FIG. 3, the current can be substantially cut off by bringing the rolls 8 to 13 into contact with a portion having no electrode. In another method, for example, an electrolytic cell is provided for the number of times of the treatment, and the electrolytic treatment is stopped at a crossing portion between the electrolytic tanks. It is needless to say that the same effect can be obtained by setting dm ² or less. By this method, the generation of coarse pits is suppressed, and the diameter of the large pits becomes substantially constant, so that a uniform rough surface can be obtained. The effect of this method is remarkable especially when an electrolytic solution mainly containing hydrochloric acid is used. If the progress of the electrolytic treatment is slow or the time required for the portion where the electrolytic treatment stops is 0.5 seconds or less, the generation of coarse pits is somewhat suppressed, but a sufficient effect of the dividing treatment cannot be obtained.
By setting it to 0.6 seconds or more, the average opening diameter of the large pit becomes 3
It is possible to obtain a rough surface having a uniform size of up to 6 μm and having no flat portion due to uneven distribution of large pits. The same effect can be obtained even if this time is lengthened. However, if the stop time is longer than 5 seconds, the productivity is remarkably reduced.

In the present invention, by using an electrolytic solution containing hydrochloric acid and acetic acid, dense small pits can be formed simultaneously with the formation of the large pits and superimposed on the large pits. The control of the small pit shape is the same as that described above. In the case of a batch type electrolytic treatment, the current density of the electrolytic power source is changed with respect to time, so that the electrolytic treatment progresses rapidly in all the electrolysis steps and the electrolysis treatment progresses slowly or stops. Are present alternately a plurality of times, the electric quantity of the electrolytic treatment in one step is 100 C / d on average.
By setting m ² or less, generation of coarse pits is suppressed,
A uniform rough surface is obtained. The current density at the portion where the progress of the electrolytic treatment is slow or stopped is 0 to 10 A / dm ² , preferably 0 to ^{2 A} / dm ² . The time when the progress of the electrolytic treatment is slow or stopped is as described above. If the time is less than 0.5 seconds, the generation of coarse pits is slightly suppressed, but a sufficient effect of the division treatment may not be obtained. By setting the average opening diameter of the large pits to be 3 to 6 μm, it is possible to obtain a rough surface having no flat portion due to uneven distribution of the large pits by setting the average opening diameter of the large pits to 0.6 μm or more. The same effect can be obtained even if this time is lengthened, but if the stop time is longer than 5 seconds, production suitability is significantly reduced.
It is preferably set to 5 seconds or less.

In the present invention, by using an electrolytic solution containing hydrochloric acid and acetic acid, dense small pits can be formed simultaneously with the formation of the large pits and superimposed on the large pits. The control of the small pit shape is the same as that described above. In the case of a batch type electrolysis process, the current density of the electrolysis power source is changed with respect to time, so that the electrolysis process progresses rapidly and the electrolysis process progresses slowly or stops in the entire electrolysis process. Are present alternately a plurality of times, the electric quantity of the electrolytic treatment in one step is 100 C / d on average.
By setting m ² or less, generation of coarse pits is suppressed,
A uniform rough surface is obtained. The current density at the portion where the progress of the electrolytic treatment is slow or stopped is 0 to 10 A / dm ² , preferably 0 to ^{2 A} / dm ² . The time when the progress of the electrolytic treatment is slow or stopped is as described above. If the time is less than 0.5 seconds, the generation of coarse pits is slightly suppressed, but a sufficient effect of the division treatment may not be obtained. By setting the average opening diameter of the large pits to be 3 to 6 μm, it is possible to obtain a rough surface having no flat portion due to uneven distribution of the large pits by setting the average opening diameter of the large pits to 0.6 μm or more. The same effect can be obtained even if this time is lengthened, but if the stop time is longer than 5 seconds, production suitability is significantly reduced.
It is preferably set to 5 seconds or less.

Further, the invention according to claim 13 or 14 is:
Preferably, the acidic electrolyte has a hydrochloric acid content of 7 to 15 g / l and an acetic acid content of 10 to 40 g / l. By including hydrochloric acid in an amount of 7 to 15 g / l, a double structure in which small pits are superimposed on large pits can be formed only by the electrolytic surface roughening treatment, and the opening diameter can be reduced by including acetic acid in an amount of 10 to 40 g / l. On the other hand, it is possible to form a pit having a small depth. If the amount of hydrochloric acid is less than 7 g / l, the large pits may become coarse even if the electrolysis is performed in a divided manner. If it exceeds 15 g / l, pits may not be formed depending on the current density and the temperature of the electrolyte, and the range of manufacturing conditions is narrowed.
If acetic acid is less than 10 g / l, the effect of forming shallow pits may be low. Even if acetic acid is added in excess of 40 g / l, the effect is not substantially improved and the meaning is reduced. Further, in this case, it is preferable that the present invention has a solubility of 1.0 to 4.0 g / m ² in alkali before electrolysis, and the acid used for neutralization includes hydrochloric acid or acetic acid. . When the amount of dissolution is less than 1.0 g / m ^2, a non-uniform structure of the surface layer of the Al raw material remains, which may adversely affect uniform pit generation in electrolysis. Even if the amount is more than 4.0 g / m ^2, there is little substantial contribution to the improvement of the uniformity in the case where the electrolysis is performed in a divided manner, which is inefficient. Further, by performing the neutralization after the alkali dissolution treatment with the same composition as the electrolytic solution of the electrolytic treatment which is the next step, the composition of the electrolytic solution is stabilized and the rough surface shape is also stabilized.

Aluminum Support The aluminum support used in the present invention includes a support made of pure aluminum and an aluminum alloy. Various aluminum alloys can be used, for example, silicon, copper, manganese,
An alloy of aluminum with a metal such as magnesium, chromium, zinc, lead, bismuth, nickel, titanium, sodium and iron is used. The aluminum support is preferably subjected to a degreasing treatment in order to remove rolling oil on the aluminum surface prior to roughening. As the degreasing process, tricrene, thinner using a solvent such as thinner, kerosene,
Emulsion degreasing treatment using an emulsion such as triethanol is used. In the degreasing treatment, an aqueous solution of an alkali such as caustic soda can be used. When an alkaline aqueous solution such as caustic soda is used for the degreasing treatment, dirt and oxide film that cannot be removed by the above degreasing treatment alone can also be removed. When an alkaline aqueous solution such as caustic soda is used for the degreasing treatment, it is preferable to perform a neutralization treatment by dipping in an acid such as phosphoric acid, nitric acid, hydrochloric acid, sulfuric acid, chromic acid, or a mixed acid thereof. When electrochemical surface roughening is performed after the neutralization treatment, it is particularly preferable to match the acid used for neutralization with the acid used for electrochemical surface roughening.

As the surface roughening of the support, electrolytic surface roughening is carried out by the method of the present invention, and a suitable amount of chemical surface roughening or mechanical surface roughening is appropriately combined as a pretreatment. The surface may be roughened. The chemical surface roughening uses an aqueous solution of an alkali such as caustic soda as in the degreasing treatment. After the treatment, it is preferable to perform a neutralization treatment by dipping in an acid such as phosphoric acid, nitric acid, hydrochloric acid, sulfuric acid, chromic acid, or a mixed acid thereof.

When electrochemical surface roughening is performed after the neutralization treatment, it is particularly preferable to match the acid used for neutralization with the acid used for electrochemical surface roughening. The mechanical surface roughening method is not particularly limited, but brush polishing and honing polishing are preferable. In brush polishing, for example, a cylindrical brush on which bristles having a bristle diameter of 0.2 to 1 mm are planted is rotated, and while a slurry in which an abrasive is dispersed in water is supplied to the contact surface, the slurry is pressed against the surface of the support to obtain a rough surface. Perform the conversion. In the honing polishing, a slurry in which an abrasive is dispersed in water is ejected under pressure from a nozzle and collides obliquely with the surface of a support to roughen the surface. Examples of the abrasive include those generally used for polishing, such as volcanic ash, alumina, and silicon carbide.
200 to # 2000, preferably # 400 to # 800.

The support having been mechanically roughened is immersed in an aqueous solution of an acid or alkali to remove abrasives, aluminum chips, etc., which have penetrated the surface of the support and to control the pit shape. Preferably, the surface is etched. Examples of the acid include sulfuric acid, persulfuric acid, hydrofluoric acid, phosphoric acid, nitric acid, hydrochloric acid, and the like, and examples of the base include sodium hydroxide, potassium hydroxide, and the like.
Among these, it is preferable to use an aqueous alkali solution. In the case where the above is immersed in an aqueous alkali solution, it is preferable to immerse in an acid such as phosphoric acid, nitric acid, sulfuric acid, chromic acid, or a mixed acid thereof to perform a neutralization treatment. When performing electrochemical surface roughening after the neutralization treatment, it is particularly preferable that the acid used for the neutralization is matched with the acid used for the electrochemical surface roughening. When performing the oxidation treatment, it is particularly preferable to match the acid used for the neutralization with the acid used for the anodic oxidation treatment.

The electrochemical surface roughening is generally performed by using an alternating current in an acidic electrolyte. An electrolytic solution containing hydrochloric acid and acetic acid is used for the electrolytic treatment. Hydrochloric acid content is 7-15g
/ L, the content of acetic acid is preferably 10 to 40 g / l. The power supply waveforms used for electrolysis are rectangular, trapezoidal,
Various waveforms such as sawtooth waves can be used,
Particularly, a sine wave is preferable.

The voltage applied in the electrochemical graining is preferably 1 to 50 V, more preferably 5 to 30 V. The current density (peak value) is 10 to 200 A / dm ²
Is preferably 20 to 150 A / dm ² .
The amount of electricity is 100 to 2000 C /
dm ² is preferable, and 200 to 1000 C / dm ² is more preferable. The temperature is preferably from 10 to 50 ° C, preferably from 15 to 45 ° C.
C is more preferred. If necessary, a nitrate, a chloride, an amine, an aldehyde, phosphoric acid, chromic acid, boric acid, oxalic acid, etc. can be added to the electrolytic solution. It is preferable to etch the surface of the support which has been electrochemically roughened by immersing it in an aqueous solution of an acid or alkali to remove smut and the like of the surface and control the pit shape. Examples of the acid include sulfuric acid, persulfuric acid, hydrofluoric acid, phosphoric acid, nitric acid, hydrochloric acid, and the like, and examples of the base include sodium hydroxide, potassium hydroxide, and the like.
Among these, it is preferable to use an aqueous alkali solution. In the case where the above is immersed in an aqueous alkali solution, it is preferable to immerse in an acid such as phosphoric acid, nitric acid, sulfuric acid, chromic acid, or a mixed acid thereof to perform a neutralization treatment. When the anodic oxidation treatment is performed after the neutralization treatment, it is particularly preferable to match the acid used for the neutralization with the acid used for the anodic oxidation treatment.

After the surface roughening treatment, an anodic oxidation treatment is performed.
The method of the anodic oxidation treatment used in the present invention is not particularly limited, and a known method can be used. An oxide film is formed on the support by the anodic oxidation treatment. In the present invention, sulfuric acid and / or phosphoric acid are used for the anodic oxidation treatment.
A method of electrolyzing at an electric current density of 1 to 10 A / dm ² using an aqueous solution containing a concentration of 〜50% as an electrolytic solution is preferably used. However, sulfuric acid described in US Pat. No. 1,412,768 is also preferable. Among them, a method of performing electrolysis at a high current density, a method of performing electrolysis using phosphoric acid described in US Pat. No. 3,511,661, and the like can be used.

After the anodic oxidation treatment, a coating layer of a metal oxide obtained by hydrolyzing and polycondensing an organic metal compound or an inorganic metal compound is provided, whereby the small pits formed by the roughening are formed. , A substantially spherical projection is formed inside.

The method of forming the roughly spherical projection is not particularly limited, but the sol containing metal oxide particles may be used.
It can be formed by applying a gel reaction solution. The sol-gel reaction solution forms a metal oxide layer by hydrolysis and polycondensation of an organic metal compound or an inorganic metal compound in an organic solvent containing water using a catalyst such as an acid or an alkali. The metal oxide particles to be bonded are firmly adhered to the substrate surface to form spherical projections.

As the metal oxide particles, alumina, titanium oxide, zirconium oxide, silica and the like can be used, and the average particle diameter is preferably 0.01 to 0.5 μm.

The organometallic compounds and inorganic metal compounds used in the sol-gel reaction solution include metal alkoxides, metal acetylacetonates, metal acetates, metal oxalates, metal nitrates, metal nitrates described in JP-A-6-35174. Sulfates, metal carbonates, metal oxychlorides, metal chlorides, and condensates obtained by partially hydrolyzing and oligomerizing these can be used alone or in combination of two or more. Among these, metal alkoxides are particularly preferred, and silicon alkoxy compounds are particularly preferred. Also, JP-A-6-3
A silane coupling agent as disclosed in JP-A-5174 may be used in combination.

As the catalyst, acids or alkalis described in JP-A-6-35174 can be used. The addition amount of the catalyst is preferably 0.05 to 5% by weight based on the total amount of the organic metal compound or the inorganic metal compound. The amount of water to be added is 0.5 to 20 with respect to the number of moles necessary for completely hydrolyzing the total amount of the organometallic compound or the inorganic metal compound.
The range of double amount is preferred.

As the organic solvent, it is preferable to use lower alcohols such as methanol, ethanol, propanol and butanol or ketones such as acetone, methyl ethyl ketone and diethyl ketone. It is preferable that the organic solvent is added in an amount suitable for promoting the reaction of the sol-gel reaction liquid, and after the reaction is advanced, an amount suitable for coating is added again.

The sol-gel reaction solution is described in JP-A-6-351.
Other compounds described in JP-A-74 may be added.

As described above, the layer of the photosensitive composition is applied on the metal oxide coating layer obtained by hydrolyzing and polycondensing the organometallic compound or the inorganic metal compound. The coating amount at this time is preferably 0.8 to 1.8 g / m ² in terms of dry weight, more preferably 1.2 to 1.6 g / m ² .
If necessary, a mat layer can be further provided thereon.

[0264]

EXAMPLES Examples 1-1 to 1-8 and Comparative Examples 1-1 to 1--1
6 << Preparation of Support >> In Table 1 below, those having an item of presence or absence of brush polishing are indicated as having a J of 0.24 mm in thickness.
The aluminum plate of IS1050 is polished with a # 800 alumina 15 wt% slurry and a cylindrical rotating nylon brush, and then immersed in a 1% aqueous sodium hydroxide solution maintained at 50 ° C. to dissolve the aluminum plate. After dissolving to 5 g / m ² and washing with water, it was immersed in an aqueous solution of the same composition as the electrolytic treatment to be performed next at 25 ° C. for 10 seconds, neutralized, and washed with water.

[0265] In the case of "No A" in the item of the presence or absence of brush polishing in Table 1, the same aluminum plate was immersed in a 1% aqueous solution of sodium hydroxide kept at 50 ° C, and the dissolution amount was 2 g / m2. after washing with water performed dissolution treatment so that the ^2, 2
An aqueous solution of the same composition as the next electrolytic treatment held at 5 ° C.
After immersion for 0 second for neutralization treatment, the substrate was washed with water.

[0266] In the case where the item "No B" is described in the item of the presence or absence of brush polishing in Table 1, the same aluminum plate was immersed in a 1% aqueous solution of sodium hydroxide kept at 50 ° C, and the dissolution amount was 2 g / m2. after washing with water performed dissolution treatment so that the ^2, 2
After immersion in a 10 g / l hydrochloric acid aqueous solution maintained at 5 ° C. for 10 seconds for neutralization, the product was washed with water.

Next, electrolytic surface roughening treatment was carried out in a 10 g / l hydrochloric acid electrolytic solution under the conditions of a temperature of 30 ° C. and a current density of 50 A / dm ^{2 by} an alternating current so that the amount of electricity to be treated was 200 C / dm ^2. Was. The sine wave AC was used as the AC power supply waveform.

Thereafter, it is immersed in a 1% aqueous solution of sodium hydroxide kept at 50 ° C., subjected to a dissolution treatment so that the dissolution amount becomes 3 g / m ² , washed with water, and then kept at 25 ° C. It was immersed in an aqueous solution of the same composition as the electrolytic treatment for 10 seconds, neutralized, and further washed with water.

[0269] In Table 1, those having no brush in the item of presence / absence of brush polishing were prepared by immersing the same aluminum plate in a 1% aqueous sodium hydroxide solution kept at 50 ° C to give a dissolution amount of 2 g / m2. after washing with water performed dissolution treatment so that the ^2, 2
It was immersed in a mixed acid aqueous solution of 10 g / l of hydrochloric acid and 20 g / l of acetic acid kept at 5 ° C. for 10 seconds to neutralize, and then washed with water.

Next, in a mixed acid electrolyte of hydrochloric acid 10 g / l and acetic acid 20 g / l, the temperature was 30 ° C., the current density was 50 A / dm ^2.
Processing quantity of electricity with an alternating current conditions 250C / dm ²
The electrolytic surface roughening treatment was performed so that The sine wave AC was used as the AC power supply waveform.

Thereafter, it is immersed in a 1% aqueous solution of sodium hydroxide kept at 50 ° C., subjected to a dissolution treatment so that the dissolution amount becomes 2 g / m ² , washed with water, and then kept at 25 ° C. It was immersed in an aqueous solution of the same composition as the electrolytic treatment for 10 seconds, neutralized, and further washed with water.

Then, the aluminum plate was subjected to electrolytic surface roughening treatment using a batch type electrolysis apparatus under the conditions of the electrolyte composition shown in Table 1, the amount of electricity processed once, and other conditions.
At this time, the distance between the electrode and the surface of the aluminum plate was 10 mm.
And After the electrolytic surface roughening, it was immersed in a 1% aqueous sodium hydroxide solution kept at 50 ° C., etched so that the dissolved amount became 2 g / m ² , and then 10% kept at 25 ° C.
It was immersed in a sulfuric acid aqueous solution for 10 seconds, neutralized, and then washed with water. Then, in a 20% sulfuric acid aqueous solution, a current density of 5 A / d
Anodizing was performed for 30 seconds under the conditions of m ² to obtain a support.

[0273]

[Table 1]

The average wavelength of undulations, the average opening diameter of large pits, the average opening diameter of small pits and the ratio of the depth to the opening diameter of small pits on the surface of the support thus obtained were measured by the methods described later. The results are shown in Table 2 below.

[0275]

[Table 2]

[0276] Next, in Table 1, those having no description in the item of presence / absence of post-treatment were not subjected to any treatment after the anodizing treatment.

[0277] Table 1 shows whether or not there is a post-treatment, and the following coating solution is applied with a wire bar on an anodic oxide film formed by anodic oxidation treatment.
For 2 minutes to form a coating layer having a dry weight of 100 mg / m ² . When the surface of the aluminum support on which such coating was performed was observed with a 10000-fold SEM photograph, it was confirmed that spherical projections having an average of 0.2 μm were formed. On the other hand, without the post-treatment, such spherical projections were not observed. Further, the space between the spherical projections was formed with a smooth surface.

<< Preparation of Coating Liquid >> Preparation of Mixture A Alumina particles were mixed and dispersed in ethyl silicate at the following weight ratio.

Alumina particles (average diameter: 0.1 μm) 50 parts by weight Tetraethyl silicate 100 parts by weight Preparation of sol-gel reaction solution The following components were stirred and reacted for about 20 minutes after the start of heat generation.

Mixture A 150 parts by weight Deionized water 30 parts by weight Methanol 25 parts by weight Phosphoric acid 0.15 parts by weight The following components were added to the liquid after the reaction to form a coating liquid. Methanol 2500 parts by weight << Measuring method >> Measurement of the average wavelength of undulation or the average opening diameter of large pits, the average opening diameter of small pits, and the ratio of the depth to the opening diameter of small pits All were measured by taking SEM photographs of the support surface.

Here, the undulations or large pits mean that all the pits have an opening diameter of not less than 3 μm and further 3
A pit having a double structure in which pits smaller than μm are present, and a small pit is a pit having an opening diameter of 3 μm or less among all pits and having no smaller pits therein.

The average wavelength of the undulations or the average opening diameter of the large pits is determined by measuring the major axis and the minor axis for each pit whose contour can be clearly discriminated using a 1000-times SEM photograph, and then averaging the wavelength or the aperture. The average was determined by dividing the sum by the total number of large pits measured.

The average opening diameter of the small pits is 5000 times S
Using an EM photograph, the average was obtained by the same method as that for the average wavelength of undulations or large pits.

The ratio of the depth to the opening diameter of the small pit is determined by using a SEM photograph of 5000 to 20,000 times the cross section.
A pit having a cross section substantially dividing the center of the pit was selected and measured.

Next, using a combination of the support and the photosensitive composition shown in Table 3 below, a coating solution of the photosensitive composition was applied to the support using a wire bar, and dried at 100 ° C. for 1 minute. A lithographic printing plate was obtained. The coating amount after drying is about 1.8 g / m ²
Met.

Photosensitive Composition A o-naphthoquinonediazidosulfonic acid ester of pyrogallol-acetone resin described in Synthesis Example 1 of JP-A-60-143345 (Mn: 1.99 × 10 ³ , Mw: 2. 95 × 10 ³ ) 1.0 g ・ Phenol-formaldehyde resin 0.7 g ・ Cresol-formaldehyde resin 2.8 g ・ Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co.) 0.1 g ・ FC-430 (manufactured by 3M, surfactant) 0.1 g-Methyl cellosolve 27 g Photosensitive composition B-O-naphthoquinonediazidosulfonic acid ester of pyrogallol-acetone resin described in Synthesis Example 3 of JP-A-60-143345 (Mn: 7.90 x 10 < ² >) ^{, Mw: 1.10 × 10 3)} 1.0g · phenol - formaldehyde resins 0.7 g · click Sol-formaldehyde resin 2.8 g Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.) 0.1 g FC-430 (3M, surfactant) 0.1 g Methyl cellosolve 27 g Photosensitive composition C O-naphthoquinonediazidosulfonic acid ester of pyrogallol-acetone resin (Mn: 2.00 × 10 ³ , Mw: 3.20 × 10 ³ ) described in Synthesis Example 4 of JP-A-60-143345 1.0 g ・ Phenol-formaldehyde Resin 0.7 g-Cresol-formaldehyde resin 2.8 g-Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.) 0.1 g-FC-430 (3M, surfactant) 0.1 g-Methyl cellosolve 27 g Photosensitive composition D. Pyrogallol described in Comparative Synthesis Example 1 of JP-A-60-143345 Of acetone resin o- naphthoquinonediazide sulfonic acid ester ^{(Mn: 2.01 × 10 3,} Mw: 4.01 × 10 3) 1.0g · Phenol - formaldehyde resins 0.7 g · cresol - formaldehyde resin 2.8 g · Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.) 0.1 g FC-430 (3M Co., surfactant) 0.1 g Methyl cellosolve 27 g Photosensitive composition E Comparative example of JP-A-60-143345 O-naphthoquinonediazidosulfonic acid ester of pyrogallol-acetone resin described in 2 (Mn: 2.99 × 10 ² , Mw: 4.98 × 10 ² ) 1.0 g ・ Phenol-formaldehyde resin 0.7 g ・ Cresol-formaldehyde Resin 2.8g ・ Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.) .1g · FC-430 (3M Co., surfactant) to the light-sensitive lithographic printing plate 0.1 g · Methyl cellosolve 27g obtained as a light source 4
Using a kW metal halide lamp, image exposure was performed for 60 seconds, and development was performed at 25 ° C. for 45 seconds with a 6-fold diluted solution of a developing solution (SDR-1, manufactured by Konica Corporation).

Table 3 shows the results of printing evaluation of the lithographic printing plates thus obtained by the following method.
Shown in

[Printing evaluation method]-Printing durability Off-press printing made by Mitsubishi Heavy Industries, Ltd. using ink (Leo Echo Black, manufactured by Toyo Ink Co., Ltd.) and dampening solution (2% aqueous solution of SG-51 manufactured by Tokyo Ink Co., Ltd.). Machine (Lissopia AY-1-130)
0) Standard printing pressure on Zara paper manufactured by Chuetsu Pulp Co., Ltd.
It indicates the number of printed sheets of normal printed matter until printing is performed at a speed of rpm and the image portion is worn and ink does not adhere and a normal printed matter cannot be obtained. The greater the number of prints, the better the printing durability.

[0289]

[Table 3]

Examples 2-1 to 2-8, Comparative examples 2-1 and 2
-6 Example 1 except that the following was used as the photosensitive composition.
-1 to 1-8 and lithographic printing plates obtained in the same manner as in Comparative Examples 1-1 to 1-6 were subjected to printing evaluation by the following method, and the results are shown in Table 4 below.

Photosensitive Composition F • 3.0 g of Exemplified Compound (1) described in Synthesis Example 1 of JP-B-52-28401 • 1,2-Naphthoquinone-2-diazido-5-sulfonic acid-phenyl ester 1 0.0 g-Methyl cellosolve 80.0 g Photosensitive composition G-4.0 g of exemplified compound (2) described in Synthesis Example 2 of JP-B-52-28401-1,2-naphthoquinone-2-diazide-5-sulfone Acid-phenyl ester 2.0 g ・ Methyl cellosolve 90.0 g Photosensitive composition H ・ Exemplified compound (5) described in Synthesis Example 4 of JP-B-52-28401 3.0 g ・ 1,2-naphthoquinone-2- 1.0 g of diazido-5-sulfonic acid-phenyl ester. 80.0 g of methyl cellosolve. Photosensitive composition I. 0.6 g of phenol-formaldehyde resin. Sol-formaldehyde resin 2.5 g 1,2-naphthoquinone-2-diazide-5-sulfonic acid-phenyl ester 1.0 g Methyl cellosolve 80.0 g Photosensitive composition J Phenol and m-, p-mixed cresol 3.5 g of a copolycondensation resin with formaldehyde (the molar ratio of phenol to cresol is 3:97) 1.0 g of 1,2-naphthoquinone-2-diazide-5-sulfonic acid-phenyl ester 80.0 g of methyl cellosolve [ Printing Evaluation Method]-Small dot reproducibility Off-press printing machine (Mitsubishi Heavy Industries, Ltd.) Lysopia AY-1-130
0) Standard printing pressure on Zara paper manufactured by Chuetsu Pulp Co., Ltd.
Printing was performed at a speed of rpm, and the dot area ratio reproducibility of 50% halftone dots on the printed matter was evaluated by measuring with a Macbeth reflection densitometer RD-918. The smaller the value is, the better the small point reproducibility is.

[0292]

[Table 4]

Examples 3-1 to 3-8 and Comparative Examples 3-1 to 3-3
-6 Example 1 except that the following was used as the photosensitive composition.
With respect to the planographic printing plates obtained in the same manner as -1 to 1-8 and Comparative Examples 1-1 to 1-6, the results of evaluating the suitability for ballpoint pens by the following method are shown in Table 5 below.

Photosensitive Composition K • Copolycondensation resin of phenol, m-, p-mixed cresol and formaldehyde (the molar ratio of phenol to cresol is 4: 6) 3.5 g • 1,2-naphthoquinone-2- Diazido-5-sulfonic acid-phenyl ester 1.2 g Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.) 0.2 g Methyl cellosolve 32.0 g Photosensitive composition L Phenol and m-, p-mixed cresol and formaldehyde 3.6 g of 1,2-naphthoquinone-2-diazide-5-sulfonic acid-α-naphthyl ester 1.5 g of Victoria Pure Blue BOH (Hodogaya 0.2g ・ Methyl cellosolve 32.0g Photosensitive composition M ・ Phenol and m-, p -Co-condensation polymerization resin of mixed cresol and formaldehyde (the molar ratio of phenol to cresol is 5: 5) 3.0 g-1,2-naphthoquinone-2-diazide-5-sulfonic acid-? -Naphthyl ester 1.5 g Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.) 0.2 g ・ Methyl cellosolve 32.0 g Photosensitive composition N ・ Phenol-formaldehyde resin 0.8 g ・ Cresol-formaldehyde resin 2.5 g ・ 1,2-Naphthoquinone-2-diazide -5-sulfonic acid-phenyl ester 1.2 g Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.) 0.2 g Methyl cellosolve 32.0 g Photosensitive composition O Phenol-formaldehyde resin 1.0 g Cresol-formaldehyde resin 2 .5 g ・ 1,2-naphthoquinone 1.5 g of 2-diazide-5-sulfonic acid-α-naphthyl ester ・ 0.2 g of Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.) ・ 32.0 g of methylcellosolve [Evaluation method] ・ Suitability of ballpoint pen After drawing the register marks on the printing plate with the register mark drawing machine, the entire surface of the photosensitive lithographic printing plate is exposed under the above conditions,
After developing, the suitability of the ballpoint pen was evaluated based on the remaining state of the ink of the pilot ballpoint pen on the grain.

：: No residue Δ: Partially ink remaining ×: Ink is clearly observed visually.

[0296]

[Table 5]

Examples 4-1 to 4-8, Comparative examples 4-1 to 4
-6 Example 1 except that the following was used as the photosensitive composition.
-1 to 1-8 and lithographic printing plates obtained in the same manner as in Comparative Examples 1-1 to 1-6 were evaluated for resistance to a fountain solution containing no isopropyl alcohol (IPA-free) by the following method. Table 6 shows the results.

Photosensitive Composition P • 1,2-Naphthoquinone-2-diazido-5-sulfonic acid-phenyl ester 1.8 g • In the general formula (2), R ₁ and R ₂ are ethoxy groups, R ₃ and R ₄ is a trichloromethyl group 0.07 g ・ Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co.) 0.07 g ・ Phenol-formaldehyde resin 1.5 g ・ Cresol-formaldehyde resin 3.0 g ・ Methyl cellosolve 100.0 g Photosensitive composition Product Q • 1,2-naphthoquinone-2-diazido-5-sulfonic acid-α-naphthyl ester 1.8 g • In the general formula (2), R ₁ and R ₂ are propoxy groups, and R ₃ and R ₄ are trichloromethyl. 0.07 g ・ Oil Blue # 603 (manufactured by Orient Chemical Industries) 0.07 g ・ Phenol-formaldehyde Resin 1.5 g-Cresol-formaldehyde resin 3.0 g-Methyl cellosolve 100.0 g Photosensitive composition R-1,2-Naphthoquinone-2-diazide-5-sulfonic acid-phenyl ester 1.8 g-General formula (2) Wherein R ₁ and R ₂ are butoxy groups and R ₃ and R ₄ are trichloromethyl groups 0.07 g ・ Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co.) 0.07 g ・ Phenol-formaldehyde resin 1.5 g ・ Cresol - formaldehyde resin 3.0 g · methyl cellosolve 100.0g photosensitive composition S · 1,2-naphthoquinone-2-diazide-5-sulfonic acid-.alpha. - in naphthyl ester 1.8 g · formula (2), R ₁ and R ₂ is ethoxy, R ₃ and 0.07 g · phenol R ₄ is trichloromethyl group - ho Lumaldehyde resin 1.5 g ・ Cresol-formaldehyde resin 3.0 g ・ Methyl cellosolve 100.0 g Photosensitive composition T ・ 1,2-Naphthoquinone-2-diazide-5-sulfonic acid-phenyl ester 1.8 g ・ Phenol-formaldehyde Resin 1.5 g-Cresol-formaldehyde resin 3.0 g-Methyl cellosolve 100.0 g [Evaluation method]-IPA-free fountain solution resistance The obtained photosensitive lithographic printing plate was exposed and developed under the conditions described above, and then IPA-free. It was immersed in a 2% aqueous solution of SG-51 (manufactured by Tokyo Ink Co., Ltd.) for 30 minutes to evaluate the degree of whitening on the image surface by visual observation.

：: No image invasion Δ: Partial whitening is observed X: Image is whitening over the entire surface.

[0300]

[Table 6]

Examples 5-1 to 5-8, Comparative examples 5-1 to 5
-6 Example 1 except that the following was used as the photosensitive composition.
Table 7 below shows the results of printing evaluation of the lithographic printing plates obtained in the same manner as in -1 to 1-8 and Comparative Examples 1-1 to 1-6 by the following method.

Synthesis of diazo resin 1 3.5 g of p-hydroxybenzoic acid and 21.75 g of p-diazodiphenylamine sulfate were dissolved in 90 g of concentrated sulfuric acid under ice-cooling. To this solution was slowly added 2.7 g of p-formaldehyde. At this time, the reaction temperature is 1
It was added not to exceed 0 ° C. After stirring the reaction solution for 2 hours, it was added dropwise to 1 liter of ethanol, and the resulting precipitate was filtered off and washed with ethanol. The precipitate was dissolved in 200 ml of pure water, and an aqueous solution in which 10.5 g of lead chloride was dissolved was added. The resulting precipitate was filtered, washed with ethanol, and then dissolved in 300 ml of pure water. In this solution, 13.
An aqueous solution in which 7 g of ammonium hexafluorophosphate was dissolved was added. The resulting precipitate was separated by filtration, washed with water and ethanol, and dried at 25 ° C. for one day to obtain diazo resin 1. When the molecular weight of this diazo resin 1 was measured by gel permeation chromatography (hereinafter abbreviated as GPC), the weight average molecular weight was about 2,300.

Synthesis of diazo resin 2 p-diazodiphenylamine sulfate of diazo resin 1 was converted to 4
-Diazo-4'-methoxydiphenylamine sulfate 2
A diazo resin 2 was obtained in the same manner as in the synthesis of the diazo resin 1, except that the amount was changed to 4.3 g. The molecular weight was measured by GPC and found to be about 2500 in weight average molecular weight.

Photosensitive Composition U • Trimethylolpropane triacrylate 0.3 g • Poly (N- (4-hydroxyphenyl) methacrylamide / acrylonitrile / methyl methacrylate / methacrylic acid) Copolymer molar ratio 25/25/42 / 8g (Mw: 42000) 0.3 g 2,4-diethylthioxanthone 0.05 g Diazo resin 1 0.02 g Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.) 0.01 g Methyl cellosolve 8.0 g Photosensitivity Composition V Pentaerythritol triacrylate 0.3 gPoly (N- (4-hydroxyphenyl) methacrylamide / acrylonitrile / methyl methacrylate / methacrylic acid) copolymer Copolymer (Mw: 25/25/40/10) in molar ratio 25/25/40/10 45000) 0. 3 g-2,4-diethylthioxanthone 0.05 g-diazo resin 1 0.02 g-Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.) 0.01 g-methyl cellosolve 8.0 g Photosensitive composition W-trimethylolpropane triacrylate 0 0.3 g ・ Poly (N- (4-hydroxyphenyl) methacrylamide / acrylonitrile / methyl methacrylate / methacrylic acid) copolymer 25/25/42/8 molar ratio copolymer (Mw: 42000) 0.3 g ・ 2,4 -Diethylthioxanthone 0.05 g-Diazo resin 2 0.02 g-Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.) 0.01 g-Methyl cellosolve 8.0 g Photosensitive composition X-Poly (N- (4-hydroxyphenyl) methacryl) Amide / acrylonitrile / methyl Tacrylate / methacrylic acid) Copolymer Copolymer with molar ratio of 25/25/42/8 (Mw: 42000) 0.6 g Diazo resin 2 0.06 g Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.) 0.01 g Methyl Cellosolve 8.0 g Photosensitive composition Y Trimethylolpropane triacrylate 0.3 g Poly (N- (4-hydroxyphenyl) methacrylamide / acrylonitrile / methyl methacrylate / methacrylic acid) copolymer molar ratio 25/25/42 / 8 copolymer (Mw: 42000) 0.3 g 2,4-diethylthioxanthone 0.05 g Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.) 0.01 g Methyl cellosolve 8.0 g [Printing evaluation method] Eye opening ink (Leo echo manufactured by Toyo Ink Co., Ltd.) Ink and a dampening solution (2% aqueous solution of SG-51 manufactured by Tokyo Ink Co., Ltd.) and a standard printing machine for Chuetsu Pulp Co., Ltd. on an off-press printing machine (Risopia AY-1-1300) manufactured by Mitsubishi Heavy Industries, Ltd. Printing pressure, 1300rpm
After printing 10,000 sheets, the ink was completely transferred to the paper surface, the printing plate was removed, and the plate was allowed to stand at room temperature and humidity for 48 hours.

After standing, printing was performed again under the same conditions, and a screen line frequency of 150 lines / inch on the printed material was changed to 8 lines.
The area of 0% halftone dot was measured with a Macbeth densitometer. The closer the measured value is to 100%, the closer the eyes are.

[0306]

[Table 7]

Examples 6-1 to 6-5, Comparative Examples 6-1 to 6
-5 The following photosensitive composition was used and used as a support.
Example 1-1, except that the image exposure with a metal halide lamp was changed to the image exposure with an exposure machine (Trendsetter 3244; semiconductor laser output 10 W, 240 channel machine) manufactured by Cleo Products Co., Ltd. For the lithographic printing plate obtained in the same manner as in Comparative Example 1-1,
Table 8 shows the results of the printing evaluation performed by the following method. Table 8 also shows the sensitivity (exposure energy at which the photosensitive layer at the exposed portion can be removed) in the image exposure.

Synthesis of Acid Decomposable Compound A 1.0 mol of 1,1-dimethoxycyclohexane, 1.0 mol of diethylene glycol, 0.003 mol of p-toluenesulfonic acid hydrate and 500 ml of toluene were stirred at 100 ° C. while stirring. After the reaction, the temperature was gradually increased to 150 ° C., and the reaction was further performed at 150 ° C. for 4 hours. Methanol generated by the reaction was distilled off during this period. After cooling, the reaction product was sufficiently washed with water, and sequentially washed with a 1% aqueous NaOH solution and a 1N aqueous NaOH solution. After washing with brine and dehydration over anhydrous potassium carbonate, the mixture was concentrated under reduced pressure. It was dried for 10 hours while heating to 80 ° C. under vacuum to obtain a wax-like compound. The weight average molecular weight Mw in terms of polystyrene measured by GPC was about 1600.

Synthesis of acid-decomposable compound B A mixture of 0.8 mol of tetraethylene glycol, 0.2 mol of p-xylylene glycol, 2.2 mol of pyridine and 800 ml of dehydrated and distilled toluene was mixed with 1.0 mol of dichlorodimethylsilane. Was added dropwise with stirring under ice-cooling. After stirring at 50 ° C. for 8 hours, the generated hydrochloride of pyridine was filtered off, and the toluene solution was concentrated under reduced pressure. Then, while heating to 80 ° C. under vacuum, 1
After drying for 0 hour, a viscous oily product was obtained. Mw is about 15
00.

Novolak resin obtained by co-condensing phenol, m-, p-mixed cresol and formaldehyde (Mw = 4000, molar ratio of phenol / m-cresol / p-cresol is 5/57 / 38) 70.0 g ・ Methyl methacrylate / hydroxyphenyl methacrylamide / methacrylamide / methacrylonitrile copolymer (copolymerization weight ratio = 20/20/30/30, Mw = 30000) 5.0 g ・ Acid decomposable compound A 20.0 g-Acid generator 3.0 g of exemplified compound (12)-Infrared absorbing dye 1.0 g of exemplified compound IR53-0.3 g of crystal violet-0.5 g of fluorine-based surfactant S-381 (manufactured by Asahi Glass)-Lactic acid Methyl 700.0 g ・ Methyl ethyl ketone 200.0 g Photosensitive composition Except that the sexual Compound A was changed to the B, to obtain a photosensitive composition have in the same manner as in <photosensitive composition Ah>.

Photosensitive composition A photosensitive composition was obtained in the same manner as the photosensitive composition except that no infrared absorbing dye was added.

Photosensitive composition A photosensitive composition was obtained in the same manner as the photosensitive composition except that no acid-decomposable compound was added.

[Printing Evaluation Method]-Off-press printing machine manufactured by Mitsubishi Heavy Industries, Ltd. using dot gain ink (Leo echo ink manufactured by Toyo Ink Co., Ltd.) and dampening solution (2% aqueous solution of SG-51 manufactured by Tokyo Ink Co., Ltd.) (Lissopia AY-1-1300)
Standard printing pressure on Zara paper manufactured by Chuetsu Pulp Co., Ltd., 1300 rpm
The printing was performed at a speed of m and the density of the image portion was 1.6, and the screen ruling was 150 lines / line on the printed material.
The area of 50% halftone dots of the inch was measured with a Macbeth densitometer, and the gain amount was calculated. The smaller the gain amount, the better.

[0314]

[Table 8]

Examples 7-1 to 7-5, Comparative Examples 7-1 to 7
-5 Examples 6-1 to 6-1 were used except that a heat treatment at 140 ° C. for 1 minute was added after the exposure and before the development before the development using the following photosensitive composition.
Table 9 shows the results of printing evaluation of the planographic printing plates obtained in the same manner as in 6-5 and Comparative Examples 6-1 to 1-5 by the following method. In this example and the comparative example, the unexposed portions of the photosensitive layer are removed by development.

A photosensitive composition was obtained in the same manner as the photosensitive composition except that the acid-decomposable compound A was changed to hexamethoxymethylolated melamine.

Photosensitive Composition A photosensitive composition was obtained in the same manner as the photosensitive composition except that the acid-decomposable compound A was changed to resol (Shownol CKP918 manufactured by Showa Kobunshi).

A photosensitive composition was obtained in the same manner as the photosensitive composition except that no infrared absorbing dye was added.

Photosensitive composition only A photosensitive composition was obtained in the same manner as the photosensitive composition except that hexamethoxymethylolated melamine was not added.

[0320]

[Table 9]

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view showing an example of an electrolytic apparatus for performing an electrolytic treatment of a support of a photosensitive lithographic printing plate according to the present invention.

FIG. 2 is a schematic cross-sectional view showing another example of an electrolysis apparatus for electrolyzing a support of a photosensitive lithographic printing plate of the invention according to claims 1 to 14;

FIG. 3 is a schematic sectional view showing still another example of an electrolytic apparatus for performing an electrolytic treatment of a support of a photosensitive lithographic printing plate according to the invention according to claims 1 to 14;

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Electrolyzer 2, 3, 4, 5 Support roll 6 Aluminum alloy plate web ax electrode

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03F 7/022 G03F 7/022 7/023 7/023 7/027 7/027 7/09 501 501 7/09 501

Claims (14)

[Claims] 1. Small pits having an average opening diameter of 0.2 to 3.0 μm are densely superimposed on large pits having a roughness of 3 to 30 μm or an average opening diameter of 3 to 30 μm. The number average molecular weight is 3.00 on an aluminum support having a substantially spherical projection having an average diameter of 0.01 μm or more and 1/2 or less of the average small pit opening diameter inside the pit.
× 10 ^{2 to} 2.00 × 10 ³ , weight average molecular weight of 5.00
A layer of a photosensitive composition containing an o-naphthoquinonediazidosulfonic acid ester of a polycondensation resin of × 10 ^{2 to} 4.00 × 10 ³ polyhydroxyphenol and a ketone or an aldehyde, and an alkali-soluble resin was provided. Features a photosensitive lithographic printing plate. 2. Small pits having an average opening diameter of 0.2 to 3.0 μm are densely superimposed on large pits having an average roughness of 3 to 30 μm or large pits having an average opening diameter of 3 to 30 μm. A structural unit represented by the following general formula (1) is formed on an aluminum support having a substantially spherical projection having an average diameter of 0.01 μm or more and 1/2 or less of the average opening diameter of small pits inside a pit. A polymer compound contained therein, and o
-A photosensitive lithographic printing plate comprising a photosensitive composition layer containing a quinonediazide compound. Embedded image (Wherein R ₁ and R ₂ are a hydrogen atom, an alkyl group or a carboxyl group, R ₃ is a hydrogen atom, a halogen atom or an alkyl group, R ₄ is a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group, and A is a nitrogen atom A divalent organic group connecting m and an aromatic ring carbon atom, m represents 0 or 1, and B represents a phenylene group which may have a substituent or a naphthylene group which may have a substituent.) 3. Small pits having an average opening diameter of 0.2 to 3.0 μm are densely superimposed on large pits having an average roughness of 3 to 30 μm or large pits having an average opening diameter of 3 to 30 μm. Phenol and m-, p are formed on an aluminum support having a substantially spherical projection having an average diameter of 0.01 μm or more and 1/2 or less of the average opening diameter of small pits inside the pit.
A resin obtained by copolycondensation of a mixed cresol and an aldehyde, wherein the mixing ratio of the phenol and the m-, p-mixed cresol is 1: 9 to 9: 1 in molar ratio;
-A photosensitive lithographic printing plate comprising a photosensitive composition layer containing a quinonediazide compound. 4. Small pits having an average opening diameter of 0.2 to 3.0 μm are densely superimposed on large pits having an average roughness of 3 to 30 μm or large pits having an average opening diameter of 3 to 30 μm. An o-quinonediazide compound represented by the following general formula (2) is formed on an aluminum support having a substantially spherical protrusion having an average diameter of 0.01 μm or more and 以下 of the small pit average opening diameter in the pit. Lithographic printing, comprising a layer of a photosensitive composition containing an s-triazine compound, a colorant that changes color by interaction with a photolysis product of the s-triazine compound, and an alkali-soluble resin. Edition. Embedded image (Wherein, R ₁ and R ₂ each represent an alkyl group, a substituted alkyl group, an alkoxy group, a substituted alkoxy group, or a hydrogen atom. R ₃ and R ₄ each represent a haloalkyl group or haloalkenyl having 1 to 3 carbon atoms. Represents a group.) 5. Small pits having an average opening diameter of 0.2 to 3.0 μm are densely superimposed on large pits having an average roughness of 3 to 30 μm or large pits having an average opening diameter of 3 to 30 μm. At least one addition-polymerizable ethylenically unsaturated double bond is formed on an aluminum support having substantially spherical projections having an average diameter of 0.01 μm or more and 以下 the average opening diameter of small pits inside the pit. A compound having an aromatic hydroxyl group in a side chain and / or a compound having an aliphatic hydroxyl group in a side chain in a molecule as a constituent unit, a soluble or swellable acidic vinyl copolymer in alkaline water, A photosensitive lithographic printing plate provided with a layer of a photosensitive composition containing a photopolymerization initiator and a diazo resin. 6. Small pits having an average opening diameter of 0.2 to 3.0 μm are densely superimposed on large pits having an average roughness of 3 to 30 μm or a large pit having an average opening diameter of 3 to 30 μm. An acid generator, an acid-decomposable compound, and an infrared absorber are contained on an aluminum support having approximately spherical projections having an average diameter of 0.01 μm or more and 1/2 or less of the average opening diameter of small pits inside the pits. A photosensitive lithographic printing plate provided with a layer of a photosensitive composition. 7. Small pits having an average opening diameter of 0.2 to 3.0 μm are densely overlapped with large pits having an average roughness of 3 to 30 μm or large pits having an average opening diameter of 3 to 30 μm. An acid generator, a compound insolubilized by an acid, and an infrared absorber are provided on an aluminum support having a substantially spherical projection having an average diameter of 0.01 μm or more and 1/2 or less of the average opening diameter of small pits inside the pit. A photosensitive lithographic printing plate comprising a layer of a photosensitive composition containing the same. 8. The small pit has an average opening diameter of 0.2 to 0.8.
μm, the average diameter of the substantially spherical projections inside the small pits is 0.
The photosensitive lithographic printing plate according to any one of claims 1 to 7, wherein the thickness is not less than 01 µm and not more than 1/4 of the average small pit opening diameter. 9. The photosensitive lithographic printing plate according to claim 8, wherein the ratio of the depth of the pit to the opening diameter of the small pit is 0.2 or less. 10. A smooth surface between the substantially spherical projections inside the small pits.
The photosensitive lithographic printing plate according to any one of Items 1 to 9, wherein: 11. The surface of an aluminum plate is mechanically roughened or degreased and then electrolytically roughened, subjected to a surface dissolving treatment with an alkali, neutralized with an acid, electrolytically roughened in an acidic electrolyte, and further alkali-lyzed. After performing a surface dissolution treatment, neutralizing with an acid and performing an anodizing treatment, a coating layer of a metal oxide obtained by hydrolysis and polycondensation of an organic metal compound or an inorganic metal compound is provided on the anodized film. A method for producing a photosensitive lithographic printing plate, comprising providing a layer of the photosensitive composition according to any one of claims 1 to 7 thereon. 12. The method for producing a photosensitive lithographic printing plate according to claim 11, wherein the electrolyte mainly comprises hydrochloric acid and / or acetic acid. 13. An aluminum plate whose surface is subjected to dissolution treatment with an alkali, neutralized with an acid, electrolytically roughened in an acidic electrolyte mainly composed of hydrochloric acid and / or acetic acid, and further, the surface is dissolved with an alkali. After neutralizing with anodizing and performing anodizing treatment, a coating layer of a metal oxide obtained by hydrolyzing and polycondensing an organic metal compound or an inorganic metal compound is provided on the anodized film, and a coating layer of the metal oxide is provided thereon. A method for producing a photosensitive lithographic printing plate, comprising providing a layer of the photosensitive composition according to any one of Items 1 to 7. 14. An electrolytic treatment in which a part where the electrolytic treatment progresses rapidly and a part where the electrolytic treatment progresses slowly or stops are alternately present a plurality of times in all the steps of electrolytic surface roughening. method for producing a photosensitive planographic printing plate of claim 13, wherein the electric quantity of the electrolytic process in progress at a faster part one step of the process is 100C / dm ² or less on average.